A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys
A new method for the standardization of osmium(IV) from chloride aqueous solutions by means of iodometric titration with visual (using starch as indicator) and potentiometric indicating of titration end point has been elaborated. This simple and rapid method is based on Os(IV) interaction with the e...
Saved in:
| Published in: | Фізико-хімічна механіка матеріалів |
|---|---|
| Date: | 2010 |
| Main Authors: | , , , |
| Format: | Article |
| Language: | English |
| Published: |
Національний Університет ім. Івана Франка
2010
|
| Online Access: | https://nasplib.isofts.kiev.ua/handle/123456789/134685 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Journal Title: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Cite this: | A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys / T. Vrublevska, M. Rydchuk, O. Bonishko, G. Mykhalyna // Фізико-хімічна механіка матеріалів. — 2010. — Т. 46, № 3. — С. 108-115. — Бібліогр.: 35 назв. — англ. |
Institution
Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1859635996071559168 |
|---|---|
| author | Vrublevska, T. Rydchuk, M. Bonishko, O. Mykhalyna, G. |
| author_facet | Vrublevska, T. Rydchuk, M. Bonishko, O. Mykhalyna, G. |
| citation_txt | A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys / T. Vrublevska, M. Rydchuk, O. Bonishko, G. Mykhalyna // Фізико-хімічна механіка матеріалів. — 2010. — Т. 46, № 3. — С. 108-115. — Бібліогр.: 35 назв. — англ. |
| collection | DSpace DC |
| container_title | Фізико-хімічна механіка матеріалів |
| description | A new method for the standardization of osmium(IV) from chloride aqueous solutions by means of iodometric titration with visual (using starch as indicator) and potentiometric indicating of titration end point has been elaborated. This simple and rapid method is based on Os(IV) interaction with the excess of iodide-ions in sulphuric acid media and on the titration of liberated iodine with the standardized solution of sodium thiosulfate. The method was approved during the determination of milligram quantities of osmium(IV) in standard solution and intermetallic alloys. Relative standard deviations (RSDs) did not exceed 1.5 %.
Розроблено нову методику стандартизації хлоридних водних розчинів осмію(IV) йодометричним титруванням з візуальною (за допомогою крохмалю) та потенціометричною фіксацією кінцевої точки титрування. Ця проста і експресна методика базується на взаємодії Os(IV) з надлишком йодид-іонів у сульфатнокислому середовищі та титруванні виділеного йоду стандартизованим розчином тіосульфату натрію. Методику апробовано під час визначення міліграмових кількостей осмію(IV) у стандартних розчинах та інтерметалічних сплавах. Похибка не перевищувала 1,5%.
Разработана новая методика стандартизации хлоридних водных растворов осмия(IV) иодометрическим титрованием с визуальной (с помощью крахмала) и потенциометрической фиксацией конечной точки титрования. Эта простая и экспрессная методика основана на взаимодействии Os(IV) с избытком иодид-ионов в сернокислой среде и титровании выделенного иода стандартизированным раствором тиосульфата натрия. Методику апробировано при определении миллиграммових количеств осмия(IV) в стандартных растворах и интерметаллических сплавах. Погрешность не превышала 1,5%.
|
| first_indexed | 2025-12-07T13:15:46Z |
| format | Article |
| fulltext |
108
Ô³çèêî-õ³ì³÷íà ìåõàí³êà ìàòåð³àë³â. – 2010. – ¹ 3. – Physicochemical Mechanics of Materials
UDC 543.2:543.5:546.94
A SIMPLE TITRIMETRIC METHOD FOR THE DETERMINATION
OF OSMIUM(IV) IN CHLORIDE STANDARD SOLUTIONS
AND INTERMETALLIC ALLOYS
T. VRUBLEVSKA, M. RYDCHUK, O. BONISHKO, G. MYKHALYNA
Ivan Franko Lviv National University, Lviv, Ukraine
A new method for the standardization of osmium(IV) from chloride aqueous solutions by
means of iodometric titration with visual (using starch as indicator) and potentiometric
indicating of titration end point has been elaborated. This simple and rapid method is
based on Os(IV) interaction with the excess of iodide-ions in sulphuric acid media and on
the titration of liberated iodine with the standardized solution of sodium thiosulfate. The
method was approved during the determination of milligram quantities of osmium(IV) in
standard solution and intermetallic alloys. Relative standard deviations (RSDs) did not
exceed 1.5 %.
Keywords: osmium(IV) hexachloride, standardization, titrimetry, potentiometry,
intermetallic alloy.
Chloride complexes of platinum group elements (PGEs) are of considerable
significance in the analytical and preparative chemistry of these elements. Particu-
larly, complex chlorides of osmium(IV) are especially important for the analytical
chemistry of osmium, since that very compounds are used for the preparation of
standard solutions, initial for osmium determination by means of instrumental
methods and for the study of osmium complexation [1, 2]. It is a known fact that in
aqueous solutions osmium may exist in various anionic forms and may readily
change its oxidation state depending on the acidity of the media, the nature and
concentration of the metal. According to the literary data [1, 2] and to our analyti-
cal practice, when Os(IV) solutions in 1...2 mol L–1 HCl are kept for a long time, a
number of additional processes may take place, particularly the processes of hydro-
lysis, aquatation or disproportionation, inherent for osmium compounds. Therefore,
in Os(IV) chloride aqueous solutions particles like Os(H2O)Cl5
–, Os(H2O)2Cl4
0
coexist next to predominant form of osmium OsCl6
2–. Moreover, if osmium(IV)
solutions from time to time are under the influence of scattered sun light, one can
observe the formation of black coloured precipitate of hydrated osmium(IV) oxide
OsO2∙2H2O [3, 4]. These factors may result in the change of concentration after
some period of storage in osmium(IV) hexachloride standard solutions, even
purchased from reputable chemical manufacturers. At the same time, it is necessary
to have osmium(IV) stock solutions with accurate concentration for the effective
routine determination of osmium by means of any instrumental technique as well
as for correct carrying out of scientific investigations of osmium compounds. That
is why the standardization, i.e. accurately checking or confirming the concentration
of osmium(IV) standard chloride solutions, is an essential part of osmium researches
and it is necessary to possess a reliable technique for the standardization of such so-
lutions. Sometimes the standard solutions of osmium(IV) hexachloride may not be
Corresponding author: T. VRUBLEVSKA, e-mail: tvrublevska@yahoo.com
mailto:tvrublevska@yahoo.com
109
purchased, taking into consideration high prices of specimens, but prepared from
other osmium compounds, e.g. from OsO4. In that case the procedure of
standardization is especially required, since the transformation of OsO4 into
OsCl6
2– can be attended by osmium losses caused by the volatility of tetraoxide.
Titrimetry is the main techniques for the standardization of PGEs solutions,
including Os [1, 5, 6]. The number of titrimetric methods for osmium determination
is not large and all of them are based on redox reactions, since these reactions run
with sufficient rate, if the conditions and reagents are correctly selected. Titrimetric
methods of osmium determination are not selective and are useful for the analyses
of standard solutions and the solutions, obtained after osmium separation from
other PGEs, as well as for relatively simple samples of few components. The end
point of titration can be rather accurately determined potentiometrically, but there
are very few methods with the visual indication of the end point.
Most titrimetric methods are proposed for the determination of Os(VIII), and
there are only few methods for Os(IV) [1, 7, 8]. Usually these methods are sug-
gested for the determination of osmium, obtained after OsO4 passing through the
reductor with metallic bismuth [1]. The reduced form of osmium (Os(IV) according
to [9]) is oxidized to osmium(VI) with a titrant, e.g. NH4VO3, an excess of which is
titrated by the standardized solution of FeSO4 [1, 8, 9]. However, vanadatometric
titration can not be utilized for the standardization of Os(IV) chloride solutions
because of few reasons. First of all, it has been established that after passing of
OsO4 sulphuric acidic solutions through the bismuth reductor, osmium is reduced
to Os(III), but not to Os(IV) [10]. Os(III) is stable in air, it is oxidized to osmium(VI)
in the media of 4...8 mol L–1 sulphuric acid with NH4VO3 (visual indication of the
end point) or to OsO4 with the stronger oxidants, e.g. KMnO4, Ce(SO4)2 (a poten-
tiometric determination of the end point) [1]. In addition, this technique was elabo-
rated for osmium evaluation from sulphuric acid solutions, but not for hydrochloric
acid (apparently, the nature of initial compound of Os is of consequence for the
titration) and it is difficult to transform osmium(IV) chloride complexes into
sulphate complexes, because they are very inactive. The matter is that OsCl6
2– is
the most kinetically inert complex among all hexachloride complexes of PGEs [1].
To convert initial osmium(IV) hexachloride into sulphate it must be heated in the
concentrated sulphuric acid at 170°C during 4...6 h [7, 11].
For the titrimetric determination of Os(IV) from acidic solutions CrSO4 is
proposed as the reducing agent [1, 8, 12]. But this method is very complicated,
because a special apparatus is necessary to store and work with CrSO4 solutions in
air free media. The permanganatometric method is suggested for the determination
of Os(IV) in alkaline media [1, 13]. Os(IV), which in the hydrochloric acid media
exists in the Н2OsСl6 form, by means of alkali is transferred into the suspension
OsО2, then it is dissolved in the presence of Н6ТеО2 and potentiometrically titrated
with the solution of KMnO4. Principal drawback of the method is the utilization of
rare and highly toxic telluric acid [14]. The drawback of a recently elaborated
titrimetric technique for the standardization of osmium(IV) solutions [15, 16] is the
need of a reagent that is not commercially available.
Since we have carried out the investigations of osmium(IV) interaction with
different azo and triphenylmethane dyes to elaborate new spectrophotometric methods
for osmium determination [17–22], we faced the problem that none of known methods
was suitable for standardization of Os(IV) stock solutions. Therefore, it has necessitated
the development of a simple, available and effective titrimetric method for the stand-
ardization of osmium(IV) chloride solutions, and it was a purpose of our study.
110
For the determination of Os(IV) from chloride aqueous solutions we have adapted
the iodometric method of the standardization of Ru(IV) chloride solutions [1, 23, 24].
The main point of this method for ruthenium determination consists of the reduction of
Ru(IV) hydroxopentachlorides with KI in the media of 2 mol L–1 HCl with following
titration of isolated I2 by means of Na2S2O3 (a visual indication of titration end point
with starch), since the amount of I2 is equal to Ru(IV) content in the sample:
2Ru4+ + 2I– → 2Ru3+ + I2 , I2 + 2S2O3
2– → 2I– + S4O6
2–.
The fact that standard redox potentials of ruthenium(IV) and osmium(IV)
chloride complexes in HCl solutions are of similar values was the principal basis
for the elaboration of the analogous method for Os(IV): E0
Ru(IV)/Ru(III)=
= E0(RuOHCl5
2–/RuH2OCl5
2–) = 0.96 V and E0
Os(IV)/Os(III) = E0(OsCl6
2–/OsCl6
3–) =
= 0.85 V [1, 7, 25] (as the matter of fact, we do not compare redox potential
E0(OsCl6
2–/OsCl6
3–) with E0(RuCl6
2–/RuCl6
3–) = 1.3 V, since Ru(IV) does not exist
in the form of hexachloride, but in the form of RuH2OCl5
2–, when the concentration
of НСІ is less than 6 mol L–1 [7]). It should be noted, that there are examples for
PGEs, when their redox potentials are not in accordance with the character of PGE
complex interaction with oxidizing or reducing agent. That is why in the analytical
chemistry of PGEs it is always necessary to take into account not only the values of
redox potentials, but also the experimental observations, when one must choose
appropriate oxidant or reductant [1].
Reagents and devices. All aqueous solutions, utilized in the research, have
been prepared,using a distilled water. All chemicals were of analytical grade.
The stock solution of Os(IV)
(H2OsCl6) was prepared by dissolving
the exact mass of OsO4 from the
hermetically sealed glass ampoule
(produced by the Corp. Aurat, Russia)
in the concentrated HCl following the
modified method [26]. The obtained
osmium solution has been kept during
one month, because according to [27],
OsO4 is rapidly reduced in the concent-
rated HCl under heating and slowly
reduced in hydrochloric acid medium at
room temperature. We wanted to avoid
the additional reduction of OsO4 with an
alcohol as well as to exclude the heating
procedure, thus preventing the possible
losses of OsO4.
The standard working Os(IV)
solutions were prepared by dissolving an
aliquot of osmium(IV) stock solution in ca. 0.5...1 mol L–1 HCl aqueous solution up to
pH<1. According to [7], OsCl6
2– does not undergo the hydrolysis in these conditions
(CHCl>0.5 mol L–1, room temperature), and according to [28], nearly 93% of Os(IV)
exists in the form of OsCl6
2– in 0.1...3 mol L–1 hydrochloric acid solutions.
The identification of Os(IV) solutions has been carried out spectrophotometri-
cally comparing electronic absorption spectra of obtained solutions with literature
data [2, 29]. As follows from the experimentally obtained spectrum (Fig. 1), in
standard stock solutions Os(IV) exists in the form of OsCl6
2–.
Fig. 1. Absorption spectrum of OsCl6
2–
solution; COs(IV) = 3.8∙10–3 mol L–1,
CHCl = 1.0 mol L–1 (A is optical density).
111
Аbsorption spectra were recorded on UV-VIS scanning spectrophotometer
SPECORD M 40 Carl Zeiss Jena (Germany) using 1 cm cuvettes. The poten-
tiometric titration was carried out with a potentiometer рН-150 М using platinum
indicator electrode ЭПЛ-02 and Ag/AgCl reference electrode ЭВЛ-1М4 (Gomel
Plant of Measuring Devices, Belarus). During potentiometric titration the solutions
were stirred with a magnetic stirrer.
Results and discussion. As it is generally known, the iodometric method of
analysis is based on the redox properties of І3
–/3І– system (Е0=0.545 V) [30, 31].
So the redox processes in iodometric determinations may be represented with the
following half-reaction:
І3
– + 2ē ↔ 3І–.
In case of iodometric titration of oxidants the reaction is carried out in acidic media,
at room temperature; KI is added in excess not only for a quantitative reaction yield, but
also for the solubilization of liberated iodine in water and for decrease of iodine volatility
due to the formation of complex ion І3
–; a reaction mixture is kept in a dark place in order
to prevent a side reaction of iodine oxidation by air oxygen (4І– + О2 + 4Н+ → 2І2 +
+ 2Н2О); for complete iodine liberation the interaction of I2 with oxidant must be carried
out for 10...15 min, as far as the reactions of oxidizing agents and KI are not very fast.
The end point in iodometric titration is usually determined using starch
solution as a visual indicator, or potentiometrically. Since starch forms with iodine
a dark blue coloured complex, so the end point is clearly defined. In case of iodine
titration with a solution of Na2S2O3 starch should be added after a moment, when
main amount of I2 is already titrated, since the adding of starch before titration
leads to overestimated results.
The method elaborated for Os(IV) determination from standard chloride solu-
tions is based of reduction Os(IV) to Os(III) with KI in sulphuric acid media. The
interaction is quantitative and sufficiently fast. As it is observed, solution of
osmium(IV) is pale yellow coloured due to OsCl6
2– [1, 32] and after adding of po-
tassium iodide the initial solution rapidly becomes greenish, what probably corresponds
to the formation of mixed chloride and iodide complexes [OsClnI6–n]2 (in [1, 33, 34]
it is reported about the existence of such complexes in aqueous solutions) as well
as to the simultaneous presence of yellow coloured complexes OsCl6
2– and OsCl6
3–
[1, 32] with a blue complex OsI6
2– [35]. After 15 min of interaction the examined
solution becomes yellowish brown as a result of I2 accumulation.
The amount of I2, liberated after the reaction with osmium, corresponds to
Os(IV) quantity in the aliquot. Therefore, in order to establish a concentration of
osmium in a sample, I2 is titrated with a standardized Na2S2O3 solution using visual
or potentiometric indication of the end point. The investigated solution again
becomes yellowish as we titrate it with Na2S2O3.
Main reactions running during the titration are described by the following equations:
2Os4+ + 2I– → 2Os3+ + I2, I2 + 2S2O3
2– → 2I– + S4O6
2–.
It is possible to determine distinctly a titration end point both visually and
potentiometricaly, moreover, during the potentiometric titration the potential value
is stabilized rapidly enough, viz. approximately in 1 minute after a next portion of
the titrant was added a sharp potential change is observed in the vicinity of the end
point even as we analyze osmium(IV) solutions with C(Os)<1 mg mL–1.
The results of iodometric determination of osmium(IV) from standard chloride
solutions with a visual indication of the titration end point by means of starch and
by potentiometric indication of the end point are presented in Table 1.
112
Table 1. The results of iodometric determination of osmium(IV) from standard chloride
solutions with visual and potentiometric indication of titration end point; n = 5; P = 0.95
Visual indication of end point Potentiometric indication of end point
Taken,
mg Os Found,
S tx
n
α×
± mg Os RSD,
%
Found,
S tx
n
α×
± mg Os RSD,
%
2.87 2.91 ± 0.02 0.6 2.87 ± 0.01 0.3
1.42 1.45 ± 0.02 1.0 1.43 ± 0.01 0.6
0.73 0.75 ± 0.01 1.0 0.72 ± 0.01 0.9
Fig. 2. Typical experimental potentiometric titration curves for iodine, liberated as a result of the
reaction with OsCl6
2–with 0.005 N Na2S2O3 solution; a – normal titration curve;
b – first derivative titration curve; c – second derivative titration curve; d – Gran plot.
Fig. 2 shows typical experimental potentiometric titration curves for iodine,
liberated after the reaction with osmium, with 0.005 N Na2S2O3 solution.
It should be mentioned that the results of Os(IV) quantification using visual
indicating of titration end point appear to be somewhat overestimated relative to
the results of potentiometric titration. It may be explained with insignificant over-
titration of solutions, which is inherent to the techniques by a visual determination
of titration end point.
As we analyzed solutions containing considerably less than 1 mg mL–1 of Os,
the distinct inflexion points for the potentiometric titration curves were not
observed, as well as clear colour change of solution from pale blue to pale yellow
during a visual indicating of the end point by means of starch, thus the results
obtained were insufficiently reproducible and accurate. Hence, the developed
method is recommended for the standardization of Os(IV) hexachloride solutions
containing milligram amounts of osmium.
We performed iodometric determination of the concentration of Os(IV)
standard chloride solutions twice a year for 5 years. The results are reproducible
113
and agree well with each other (Table 2). Therefore, we confirmed experimentally
that under proper conditions of OsCl6
2– solutions storage the concentration of initial
standard solution 0.379 mol L–1 changed only in the thousandth parts of
concentration units, viz. no more than by ca. 1%.
Table 2. The results of the concentration estimation for initial standard chloride
solutions of osmium(IV) in 2005–2009
Date of
examination 2005 2006 2007 2008 2009
СOs ± ΔС,
mol L–1 0.379±0.002 0.377±0.001 0.376±0.001 0.374±0.002 0.373±0.001
RSD, % 0.4 0.2 0.3 0.5 0.2
A good repeatability and reproducibility of the results of reiterated titrations suggest
the accuracy of the introduced technique for the standardization of Os(IV) solution.
Also we have applied the developed titrimetric method for the estimation of
osmium content in the samples of tri-component intermetallic alloys Nd20Os15Sі65
and Nd10Os30Sі60. The procedure of dissolution of intermetallide samples was as
follows: 0.2...0.5 g of the intermetallic alloy was dissolved in 10...20 mL of a
mixture of concentrated НСl and HNO3 (10:1) and heated in a beaker on the sand
bath for 1...2 h. Under these conditions a gray-coloured residue (elemental
silicium) was formed on the bottom of the beaker. After quantitative transfer of the
solution into a 100.0 mL volumetric flask the residue was washed with 1 mol L–1
NaOH solution for a few times. The washing liquid was placed into the same flask
and distilled water was added to complete the volume to 100.0 mL. Since
neodymium and silicium, present in the intermetallide samples, did not interfere in
osmium(IV) interaction with KI, the alloy was analyzed directly after the
dissolution. For the analytical procedure the 0.5...2.0 mL of analytes aliquots were
taken. The results are presented in Table 3. The obtained findings correlate well
with the nominal osmium content, i.e. calculated in the accordance with atomic per
cents in the alloys. The accuracy and reproducibility of the results of Os iodometric
determination in these samples are better than of the ones obtained by means of
spectrophotometric methods with organic reagents [19, 20].
Table 3. The results of iodometric determination of osmium in intermetallic alloys;
n = 5; P = 0.95
Visual indication
of end point
Potentiometric indication
of end point
Intermetallide ωOs
nominal,
% w/w
pr
Os
S t
n
α⋅
ω ± ,
% w/w
RSD,
%
pr
Os
S t
n
α⋅
ω ± ,
% w/w
RSD,
%
Nd20Os15Sі65 37.7 38.2 ± 0.7 1.4 38.0 ± 0.5 1.0
Nd10Os30Sі60 64.6 65.3 ± 1.0 1.2 65.1 ± 0.8 0.9
The developed method for the determination of Os(IV) from chloride aqueous
solutions provides such advantages in comparison with other actual methods: the
method is simple and rapid; it is suitable for the direct analysis of chloride
osmium(IV) solutions; there is no necessity to use special equipments, as well as
rare and toxic chemicals or organic solvents; experimentally obtained results are
correct and reproducible. That is why this titrimetric method of Os(IV) solutions
standardization can be useful for chemists, who deal both with the researches of
osmium compounds and with osmium quantification.
114
Procedure of the osmium(IV) determination. An aliquot of osmium(IV)
chloride standard solution (or a solution of intermetallic alloy) containing ca. 1 mg
of osmium was placed into Erlenmeyer flask. Then 10 mL of 2 mol L–1 sulphuric
acid and 5 mL 10% w/w KI solution, which did not contain free iodine, were
added. The flask was covered with a watch glass and put into a dark place for
15 min. After that a watch glass was washed with distilled water over the flask.
Isolated I2 was then titrated with 0.005 N sodium thiosulphate, standardized after
K2Cr2O7. Titration was carried out at room temperature.
Titration end point was evaluated with a visual indicator (liberated iodine was
titrated with Na2S2O3 solution to pale yellow colour of the solution, then 1 mL of
freshly prepared 0.5% w/w solution of starch was added and the titration was
continued, until the colour change from blue to straw was observed after the
addition of 1 drop of sodium thiosulphate solution), as well as potentiometrically
(using Pt indicator electrode and Ag/AgCl reference electrode and the end point
was located from the obtained potentiometric titration curves).
In order to obtain reproducible results titration procedures were repeated
several times.
CONCLUSIONS
The iodometric method for the determination of milligram quantities of
Os(IV) from chloride aqueous solutions has been elaborated. The method was
successively approved to estimate the exact concentration of Os(IV) in standard
solutions and to establish osmium content in the intermetallic alloys.
РЕЗЮМЕ. Розроблено нову методику стандартизації хлоридних водних розчинів ос-
мію(IV) йодометричним титруванням з візуальною (за допомогою крохмалю) та потенціо-
метричною фіксацією кінцевої точки титрування. Ця проста і експресна методика базу-
ється на взаємодії Os(IV) з надлишком йодид-іонів у сульфатнокислому середовищі та
титруванні виділеного йоду стандартизованим розчином тіосульфату натрію. Методику
апробовано під час визначення міліграмових кількостей осмію(IV) у стандартних розчи-
нах та інтерметалічних сплавах. Похибка не перевищувала 1,5%.
РЕЗЮМЕ. Разработана новая методика стандартизации хлоридних водных растворов ос-
мия(IV) иодометрическим титрованием с визуальной (с помощью крахмала) и потенциомет-
рической фиксацией конечной точки титрования. Эта простая и экспрессная методика осно-
вана на взаимодействии Os(IV) с избытком иодид-ионов в сернокислой среде и титровании
выделенного иода стандартизированным раствором тиосульфата натрия. Методику апроби-
ровано при определении миллиграммових количеств осмия(IV) в стандартных растворах и
интерметаллических сплавах. Погрешность не превышала 1,5%.
1. Аналитическая химия платиновых металлов / С. И. Гинзбург, Н. А. Езерская, В. П. Про-
кофьева и др. – М.: Наука, 1972.
2. Алимарин И. П., Хвостова В. П., Кадрова Г. И. Поведение и состояние соединений
осмия (VIII), (VI) и (IV) в водных растворах, используемых в аналитической химии //
Журн. аналит. хим. – 1975. – 30, № 10. – P. 2007–2018.
3. Хвостова В. П., Кадырова Г. И., Алимарин И. П. Исследование состояния осмия (IV) в
солянокислых растворах // Изв. АН СССР. Сер. хим. – 1977. – 11. – P. 2418–2422.
4. Kulprathipanja S., Hnatovich D. J., and Treves S. The hydrolysis and radiolysis of 191Os
hexachloroosmate(IV) // J. Inorg. Nucl. Chem. – 1977. – 39, № 6. – P. 933–935.
5. Van Loon J. C. and Barefoot R. R. Determination of the Precious Metals. Selected
Instrumental Methods // J. Wiley and Sons. – UK: Chichester, 1991.
6. Rao C. R. M. and Reddi G. S. Platinum group metals (PGM); occurrence, use and recent
trends in their determination // Trends in Anal. Chem. – 2000. – 19, № 9. – P. 565–586.
7. Золотов Ю. А., Варшал Г. В., Иванов В. М. Aналитическая химия металлов платино-
вой группы. – М.: Едиториал УРСС, 2003.
8. Beamish F. E. Analytical Chemistry of Noble Metals. Part 2. – New York: Pergamon, 1969.
9. Сырокомский В. С. Новый объемно-аналитический (ванадатометрический) метод оп-
ределения осмия // Докл. АН СССР, ОХН. – 1945. – 46, № 7. – P. 307–309.
115
10. Santrûček J., Nêmec J., Zýka J. Oxydimetrische Osmiumbestimmung Im Sauren Medium //
J. Coll. Czech. Chem. Comm. – 1966. – 31. – P. 2679–2685.
11. Синицын Н. М., Бондарь Н. М., Новицкий Г. Г. О химическом состояние осмия в серно-
кислых растворах // Журн. неорг. хим. – 1992. – 37, № 10. – P. 2199–2204.
12. Crowell W. R. and Baumbach H. L. The potentiometric determination of quadrivalent
osmium with chromous sulfate // J. Am. Chem. Soc. – 1935. – 57, № 12. – P. 2607–2609
13. Santrûček J., Nêmec J., Zýka J. Oxydimetrische Bestimmung des Osmiums in Alkalischem
Medium // Mikrochim. Acta. – 1966. – 54, № 1–2. – P. 10–16.
14. Вредные вещества в промышленности. Справочник для химиков, инженеров и врачей.
Т. III. Неорганические и элементорганические соединения. Под ред. Н. В. Лазарева и
И. Д. Гадаскиной. – Ленинград: Химия, 1977.
15. Chmilenko F. A. and Khudyakova S. N. Complexation of Osmium(IV) with 3-Methyl-2,6-Dimer-
capto-1-Thiopyrone-4 and Its Catalytic Application // J. Anal. Chem. – 60, № 11. – P. 1014–1018.
16. Chmilenko F. A. and Khudyakova S. N. Titrimetric Determination of Small Amounts of
Osmium in the Gas Condensate and Mine Water // J. Water Chem. Techn. – 2008. – 30,
№ 3. – P. 157–160.
17. Врублевська Т. Я., Бонішко О. С. Спектрофотометрія комплексів Os(IV) з метилтимо-
ловим синім // Вопр. хим. хим. техн. – 2006. – 1. – P. 8–12.
18. Cпектрофотометричне дослідження взаємодії іонів осмію (IV) з тропеоліном О /
О. С. Бонішко, М. В. Полько, О. Я. Коркуна, Т. Я. Врублевська // Вісн. Харків. ун-ту.
Сер. Хім. – 2007. – 15(38), № 770. – P. 70–75.
19. Spectrophotometric determination of osmium(IV) ions in intermetallic compounds / O. S. Bo-
nishko, T. Ya. Vrublevska, O. Z. Zvir, and O. P. Dobryanska // Materials Science. – 2008.
– 44, № 2. – P. 248–253.
20. Spectrophotometric methods for osmium determination using organic reagents: application
to intermetallides / M. V. Rydchuk, G. M. Mykhalyna, O. S. Bonishko, O. P. Dobryanska,
and T. Ya. Vrublevska // Chemistry of Metals and Alloys. – 2009. – 2. – P. 89–93.
21. Ридчук М. В., Врублевська Т. Я., Коркуна О. Я. Тропеолін ООО-ІІ – аналітичний
реагент для спектрофотометричного визначення Os(IV) // Вопр. хим. хим. техн.
– 2009. – 5. – P. 75–81.
22. Application of orange G as a complexing reagent in spectrophotometric determination of
osmium(IV) / M. Rydchuk, T. Vrublevska, O. Korkuna, and M. Volchak // Chem. Anal.
(Warsaw). – 2009. – 54. – P. 1051–1063.
23. Автократова Т. Д. Аналитическая химия рутения. – М.: Изд-во АН СССР, 1962.
24. Crowell W. and Jost D. The Oxidation States of Ruthenium in Its Halide Compounds // J.
Am. Chem. Soc. – 1928. – 50, № 2. – P. 374–378.
25. Лурье Ю. Ю. Справочник по аналитической химии. – М.: Химия, 1989.
26. Turner A. G., Clifford A. F., and Ramachandra Rao C. N. Crystallographic Data. 174.
Potassium Hexachloro-osmate, K2OsCl6, and Potassium Hexabromo-osmate, K2OsBr6
// Anal. Chem. – 1958. – 30, № 10. – P. 1708–1709.
27. Balcerzak M., and Świecicka E. Determination of ruthenium and osmium in each others
presence in chloride solutions by direct and third-order derivative Spectrophotometry
// Talanta. – 1996. – 43, № 3. – P. 471–478.
28. Москвин Л. Н., Шматко А. Г. Кинетика реакций замещения лигандов [OsCl6]2– и
[Os(Н2О)Cl5]– в растворах HCl // Журн. неорг. хим. – 1988. – 33, № 3. – P. 1229–1234.
29. Miano R. R. and Garner C. S. Kinetics of Aquation of Hexachloroosmate(IV) and Chloride
Anation of Aquopentachloroosmate(IV) Anions // Inorg. Chem. – 1965. – 4, № 3. – P. 337–342.
30. Harvey D. Modern Analytical Chemistry. – McGraw-Hill, Boston, 2000.
31. Золотов Ю. А. Основы аналитической химии. Ч. 2. Методы химического анализа.
– М.: Высш. шк., 1996.
32. Ливинстон С. Химия рутения, родия, палладия, осмия, иридия, платины. – М.: Мир,
1978.
33. Preetz W. and Homborg H. Darstellung von Chloro-Jodo-Osmaten(IV) Einschließlich der
Cis-Trans-Isomeren // J. Inorg. Nucl. Chem. – 1970. – 32, № 6. – P. 1979–1984.
34. Jørgensen C. K., Preetz W., and Homborg H. Electron transfer spectra of osmium(IV) mixed
chloro-iodo and bromo-iodo complexes // Inorg. Chim. Acta. – 1971. – 5. – P. 223–230.
35. Norman A. F. and Nebel B. R. The Quantitative Determination of Osmium Tetroxide in
Fixatives // Biotechnic and Histochemistry. – 1962. – 37, № 6. – P. 347–350.
Received 26.04.2010
|
| id | nasplib_isofts_kiev_ua-123456789-134685 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 0430-6252 |
| language | English |
| last_indexed | 2025-12-07T13:15:46Z |
| publishDate | 2010 |
| publisher | Національний Університет ім. Івана Франка |
| record_format | dspace |
| spelling | Vrublevska, T. Rydchuk, M. Bonishko, O. Mykhalyna, G. 2018-06-14T06:55:27Z 2018-06-14T06:55:27Z 2010 A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys / T. Vrublevska, M. Rydchuk, O. Bonishko, G. Mykhalyna // Фізико-хімічна механіка матеріалів. — 2010. — Т. 46, № 3. — С. 108-115. — Бібліогр.: 35 назв. — англ. 0430-6252 https://nasplib.isofts.kiev.ua/handle/123456789/134685 543.2:543.5:546.94 A new method for the standardization of osmium(IV) from chloride aqueous solutions by means of iodometric titration with visual (using starch as indicator) and potentiometric indicating of titration end point has been elaborated. This simple and rapid method is based on Os(IV) interaction with the excess of iodide-ions in sulphuric acid media and on the titration of liberated iodine with the standardized solution of sodium thiosulfate. The method was approved during the determination of milligram quantities of osmium(IV) in standard solution and intermetallic alloys. Relative standard deviations (RSDs) did not exceed 1.5 %. Розроблено нову методику стандартизації хлоридних водних розчинів осмію(IV) йодометричним титруванням з візуальною (за допомогою крохмалю) та потенціометричною фіксацією кінцевої точки титрування. Ця проста і експресна методика базується на взаємодії Os(IV) з надлишком йодид-іонів у сульфатнокислому середовищі та титруванні виділеного йоду стандартизованим розчином тіосульфату натрію. Методику апробовано під час визначення міліграмових кількостей осмію(IV) у стандартних розчинах та інтерметалічних сплавах. Похибка не перевищувала 1,5%. Разработана новая методика стандартизации хлоридних водных растворов осмия(IV) иодометрическим титрованием с визуальной (с помощью крахмала) и потенциометрической фиксацией конечной точки титрования. Эта простая и экспрессная методика основана на взаимодействии Os(IV) с избытком иодид-ионов в сернокислой среде и титровании выделенного иода стандартизированным раствором тиосульфата натрия. Методику апробировано при определении миллиграммових количеств осмия(IV) в стандартных растворах и интерметаллических сплавах. Погрешность не превышала 1,5%. en Національний Університет ім. Івана Франка Фізико-хімічна механіка матеріалів A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys Простой титрометрический метод для определения осмия(IV) в стандартных хлоридных растворах и интерметаллических сплавах Простий титрометричний метод для визначення осмію(IV) в стандартних хлоридних розчинах та інтерметалічних сплавах Article published earlier |
| spellingShingle | A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys Vrublevska, T. Rydchuk, M. Bonishko, O. Mykhalyna, G. |
| title | A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys |
| title_alt | Простой титрометрический метод для определения осмия(IV) в стандартных хлоридных растворах и интерметаллических сплавах Простий титрометричний метод для визначення осмію(IV) в стандартних хлоридних розчинах та інтерметалічних сплавах |
| title_full | A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys |
| title_fullStr | A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys |
| title_full_unstemmed | A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys |
| title_short | A simple titrimetric method for the determination of osmium(IV) in chloride standard solutions and intermetallic alloys |
| title_sort | simple titrimetric method for the determination of osmium(iv) in chloride standard solutions and intermetallic alloys |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/134685 |
| work_keys_str_mv | AT vrublevskat asimpletitrimetricmethodforthedeterminationofosmiumivinchloridestandardsolutionsandintermetallicalloys AT rydchukm asimpletitrimetricmethodforthedeterminationofosmiumivinchloridestandardsolutionsandintermetallicalloys AT bonishkoo asimpletitrimetricmethodforthedeterminationofosmiumivinchloridestandardsolutionsandintermetallicalloys AT mykhalynag asimpletitrimetricmethodforthedeterminationofosmiumivinchloridestandardsolutionsandintermetallicalloys AT vrublevskat prostoititrometričeskiimetoddlâopredeleniâosmiâivvstandartnyhhloridnyhrastvorahiintermetalličeskihsplavah AT rydchukm prostoititrometričeskiimetoddlâopredeleniâosmiâivvstandartnyhhloridnyhrastvorahiintermetalličeskihsplavah AT bonishkoo prostoititrometričeskiimetoddlâopredeleniâosmiâivvstandartnyhhloridnyhrastvorahiintermetalličeskihsplavah AT mykhalynag prostoititrometričeskiimetoddlâopredeleniâosmiâivvstandartnyhhloridnyhrastvorahiintermetalličeskihsplavah AT vrublevskat prostiititrometričniimetoddlâviznačennâosmíûivvstandartnihhloridnihrozčinahtaíntermetalíčnihsplavah AT rydchukm prostiititrometričniimetoddlâviznačennâosmíûivvstandartnihhloridnihrozčinahtaíntermetalíčnihsplavah AT bonishkoo prostiititrometričniimetoddlâviznačennâosmíûivvstandartnihhloridnihrozčinahtaíntermetalíčnihsplavah AT mykhalynag prostiititrometričniimetoddlâviznačennâosmíûivvstandartnihhloridnihrozčinahtaíntermetalíčnihsplavah AT vrublevskat simpletitrimetricmethodforthedeterminationofosmiumivinchloridestandardsolutionsandintermetallicalloys AT rydchukm simpletitrimetricmethodforthedeterminationofosmiumivinchloridestandardsolutionsandintermetallicalloys AT bonishkoo simpletitrimetricmethodforthedeterminationofosmiumivinchloridestandardsolutionsandintermetallicalloys AT mykhalynag simpletitrimetricmethodforthedeterminationofosmiumivinchloridestandardsolutionsandintermetallicalloys |