Precipitation of bismuth(III) salicylates from mineral acid solutions

Article abstract of DOI:10.1134/S0036023609060096

Powder X-ray diffraction, IR spectroscopy, Raman spectroscopy, thermogravimetry, and chemical analysis were used to study the precipitation of bismuth(III) salicylates from perchloric, nitric, and hydrochloric acid solutions as dependent on the salicylate

Full text of DOI:10.1134/S0036023609060096

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2009, Vol. 54, No. 6, pp. 873–880. © Pleiades Publishing, Inc., 2009.
Original Russian Text © E.V. Timakova, T.A. Udalova, Yu.M. Yukhin, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 6, pp. 937–944.
SYNTHESIS AND PROPERTIES
OF INORGANIC COMPOUNDS
Precipitation of Bismuth(III) Salicylates
from Mineral Acid Solutions
E. V. Timakova, T. A. Udalova, and Yu. M. Yukhin
Institute of Solid-State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences,
pr. Kutateladze 18, Novosibirsk, 630128 Russia
Received March 25, 2008
Abstract—Powder X-ray diffraction, IR spectroscopy, Raman spectroscopy, thermogravimetry, and chemical
analysis were used to study the precipitation of bismuth(III) salicylates from perchloric, nitric, and hydrochloric
acid solutions as dependent on the salicylate ion concentration, temperature, and pH. Depending on the synthe-
sis parameters, precipitation from perchloric and nitric acid solutions yields monosalicylate BiOC7H5O3 or
disalicylate Bi2O(C7H5O3)4.
DOI: 10.1134/S0036023609060096
Bismuth compounds are used in medicine for treat- medications are also enveloping and antimicrobial
ment of various gastrointestinal diseases since the end agents. They are active against Helicobacter pylori,
of the 18th century. The first liquid preparation contain- which plays the key role in chronic gastritis, ulcer, and
ing bismuth subsalicylate as the drug substance was stomach cancer.
developed in 1900 in the United States.
It is pertinent to study the composition of bismuth
compounds with various anions that precipitate from
perchloric acid solutions. When bismuth perchlorate
solutions are diluted with water, basic bismuth salts do
not precipitate, unlike in other solutions of bismuth
salts [13]. Therefore, the contamination of precipitates
with bismuth compounds of mineral acid anions is
avoided here. Inasmuch as bismuth(III) compounds are
usually prepared by precipitation from nitric acid solu-
tions, it is of practical interest to study the precipitation
of basic bismuth salicylate directly from nitric acid
solutions and from hydrochloric acid solutions, which
are used in hydrometallurgy of bismuth.
Salicylic acid and many of its derivatives are widely
used as drugs [2]. Salicylic acid is bibasic, thus forming
diverse complexes with metals. In acid and neutral solu-
tions, salicylic acid exists as ë6ç4éçëéé– (HSal–) ions
and undissociated molecules. In alkaline solutions,
ë6ç4éëéé2– (Sal2–) doubly charged ions are formed.
Thus, the compounds of salicylic acid with metals are
categorized into two groups depending on whether they
contain HSal– or Sal2– anions [3].
Various bismuth compounds of salicylic acid are
described in the literature. For example, basic bismuth
salicylates containing one salicylic acid anion per bis-
muth(III) cation can form: C6H4(OH)COOBiO [4],
C7H5BiO4 [5], and C6H4(OH)COOBi(OH)2 [6]. The
composition of basic bismuth salicylate is also repre-
sented as a mixture with oxide ([C6H4(OH)COOBi +
Bi2O3] [7]) or as a compound containing one and a half
salicylic acid anions ((C7H5O3)6Bi4O3 [8]) or two sali-
cylic acid anions [9]. Neutral compounds containing
three salicylic acid ions (C7H5O3)3Bi [10] and
(C7H5O3)3Bi · 4H2O [8]) and neutral bismuth salicylate
(Bi2(C6H4OHCOO)3 [11]) have also been documented.
Here, we present the results of our study of the effect
of salicylate ion concentration, temperature, and pH on
the percentage bismuth precipitation from perchloric,
nitric, and hydrochloric acid solutions and on the com-
position of the products.
EXPERIMENTAL
The mineral acids, salts, and alkalis used in this
work were of chemically pure or high purity grade. The
initial solutions of bismuth perchlorate (900 g/L), bis-
muth nitrate (420 g/L), and bismuth chloride (230 g/L)
were prepared by dissolving bismuth oxide (os.ch. 13-3
grade) in 6 M perchloric, nitric, and hydrochloric acid,
respectively.
Basic bismuth salicylate (bismuth subsalicylate) is a
widely used antiulcer pharmaceutical [12]. This com-
pound is an odorless and tasteless white powder and is
insoluble in water and ethanol. Basic bismuth salicylate
Hydrolytic precipitation of bismuth from solutions
is the drug substance of antiulcer and antidiarrhea med- was carried out in Teflon vessels equipped with stirrers;
ications Desmol, Pepto-Bismol, and Bismatrol. These the vessels were thermostated on WB-2 water baths. To
873

874
TIMAKOVA et al.
nitrate ions in solid reaction products were determined
R
after they were solubilized by 2 M NaOH at 70–90°ë.
Salicylate ions and free salicylic acid in precipitates
were determined photocolorimetrically [15]. Free sali-
cylic acid was determined after it was solubilized by
ethanol. Nitrate ions were determined photometrically
with sodium salicylate [16].
100
80
60
40
20
4
5
3
RESULTS AND DISCUSSION
2
Our experiments to precipitate basic bismuth salicy-
late by sodium salicylate solutions from perchloric acid
solutions at 23 and 70°ë (Fig. 1; curves 1, 2) or by sal-
icylic acid solutions at 70°ë (Fig. 1, curve 3) showed
that the percentage bismuth precipitation depends on
the amount of salicylate ions and temperature. As the
salicylate ion concentration or temperature increases,
the percentage bismuth precipitation (R) also increases.
When the mole ratio of salicylate ions to bismuth in
solution (n) is 1.0, the percentage bismuth precipitation
is (1) 83.1, (2) 95.8, and (3) 91.7%. As n increases to
1.1, the percentage bismuth precipitation increases to
94.5, 99.9, and 96.5%, respectively. When bismuth is
precipitated from nitric or hydrochloric acid solutions,
the percentage precipitation also increases with salicy-
late ion concentration; it is at least 99.0% for n = 4 in
nitric acid solutions (Fig. 1, curve 4) and for n = 6 in
hydrochloric acid solutions (Fig. 1, curve 5).
Chemical analyses of the products of bismuth pre-
cipitation by sodium salicylate from perchloric acid
solutions at 70°ë with n varied from 0.25 to 6
(pH increases from 1.4 to 4.4, respectively) indicate
that these precipitates are bismuth monosalicylate
BiC7H5O4. The analyses were as follows (%): bismuth,
57.6 (calcd., 57.7); salicylate ion, 37.6 (calcd., 37.9);
free salicylic acid, at most 0.2%; and n = 1.0. The com-
pound has characteristic X-ray diffraction peaks with
d/n of 2.38, 2.78, 2.83, 3.33, 3.46, 3.68, 3.77, 4.16, 4.60,
5.43, 7.42, 8.30, 10.2, 11.0, and 16.4 (Fig. 2 curve a).
The precipitates obtained at 23°ë are also bismuth
monosalicylate as identified by chemical analysis and
X-ray powder diffraction; the admixture of free sali-
cylic acid increases with increasing n because of the
low water solubility of salicylic acid under ambient
temperature and pressure [17].
1
0
1
2
3
4
5
6
n
Fig. 1. Percentage bismuth(III) precipitation R (%) vs. mole
ratio of salicylate ions to bismuth(III) n in (1–3) perchloric,
(4) nitric, and (5) hydrochloric acid solutions upon addition
of (1, 2, 4, 5) sodium salicylate and (3) salicylic acid to the
bismuth-containing solution. Temperature, °C: (1) 23 and
(2–5) 70.
precipitate basic bismuth salicylate from perchloric,
nitric, and hydrochloric acid solutions, the proper bis-
muth-containing solution was added to an aqueous
solution of sodium salicylate or salicylic acid. The ratio
of the volumes of the initial and final solutions was 1 :
10; this ratio was adjusted with distilled water. The
mixture was stirred for 1 h. The precipitate was filtered
off, washed with distilled water, and dried in air.
Powder X-ray diffraction analysis of precipitation
products was carried out on a DRON-3 diffractometer
(CuKα radiation; counter speed: 0.5 deg/min). Differen-
tial thermal analysis (DTA) and weight loss (TG)
curves were recorded on an MOM derivatograph; the
heating rate was 10 K/min. Absorption spectra in the IR
range (400–4000 cm–1) were recorded as disks with cal-
cined KBr on a Specord IR-75 spectrophotometer.
Raman spectra were recorded on a Bruker FT–Raman
spectrometer model RFS 100/S equipped with an
Nd:YAG laser (maximal power: 5 W; laser wavelength:
1.64 µm). Electron micrographs were obtained using a
JEM-2000FXII transmission electron microscope
(accelerating voltage: 200 kW). pH was measured on
an OP-264/1 pH meter with a glass electrode. Specific
surface areas were measured chromatographically as
thermal argon desorption.
Inasmuch as salicylic acid is dibasic (in acid and
neutral solutions, it dissociates with the elimination of
carboxyl proton (ä1 = 2.8), and in alkali solutions,
with the elimination of the phenolic hydroxide proton
Bismuth(III) macroconcentrations in solutions were (ä2 = 13.4) [18]), we studied the percentage bismuth
titrated with complexone III with the Xylenol Orange
indicator. Bismuth(III) microconcentrations were
determined photocolorimetrically with sodium iodide
[14]. Precipitation products were dissolved in dilute
HNO3 (1 : 1) under heating. Salicylate anions and
precipitation and the composition of precipitates as
affected by solution pH in order to substitute bismuth-
containing cations for the two protons of salicylic acid.
In these experiments, an alkali solution of sodium sali-
cylate was added to perchloric acid solutions of bis-
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PRECIPITATION OF BISMUTH(III) SALICYLATES
875
muth with n = 0.5. After the system was alkalinized
until its equilibrium pH was 1.4, bismuth monosalicy-
late precipitated. When equilibrium pH was 3.7 and 8.8,
precipitates were X-ray amorphous and the ratio of sal-
icylate ions to bismuth was 0.82 and 0.50, respectively.
IR and Raman spectra did not contain characteristic
bands of doubly deprotonated salicylate anions. There-
fore, the samples synthesized under the specified con-
ditions are likely mixtures of bismuth monosalicylate
and oxohydroxoperchlorate.
‡
When salicylic acid was used to precipitate bismuth
from perchloric acid solutions at 70°ë, the precipitates
with n ranging from 0.25 to 1.5 were identified by
X-ray diffraction with bismuth monosalicylate. The
precipitate prepared with n = 1.0 contained 57.1% bis-
muth, 37.8% salicylate ions, and 0.13% free salicylic
acid. Thus, salicylic acid precipitates bismuth as
monosalicylate with n varied from 0.25 to 1.5. As the
ratio of salicylate ions to bismuth in solution increased
to 2, the precipitate contained 46.6% bismuth and
45.7% salicylate ion; the ratio of salicylate ions to bis-
muth in the precipitate was 1.5. The X-ray diffraction
pattern for the precipitate contained peaks from bis-
muth monosalicylate and extra peaks with d/n: 1.88,
2.06, 2.26, 2.31, 2.73, 3.15, 3.26, 3.99, 4.31, 4.44, 4.54,
4.99, 6.14, 6.77, 7.48, and 14.9 (Fig. 2, curve b). These
peaks are the major ones for compounds prepared with
n increasing from 3 to 4 (Fig. 2, curve c). For example,
the precipitates prepared with n = 3 and 4 contained
41.9% bismuth (calcd., 42.5%) and 55.9% salicylate
ions (calcd., 55.8%); the stoichiometric ratio of salicy-
late ions to bismuth was 2.0, corresponding to the for-
mation of bismuth disalicylate. Chemical analysis, IR,
and Raman spectra showed that the aqueous ethanol
treatment of the precipitates at room temperature did
not change the product composition. The X-ray diffrac-
tion patterns of the products do not contain peaks from
free salicylic acid, d/n: 2.26, 2.37, 2.46, 2.54, 2.58,
2.74, 2.81, 2.93, 3.12, 3.21, 3.56, 5.22, 5.91, and 8.22.
Our experiments also show that, when the mole ratio
of salicylate ions to bismuth increases to 5–20, the pre-
cipitation products are mixtures of bismuth disalicylate
and salicylic acid. This is verified by powder X-ray dif-
fraction, IR spectroscopy, Raman spectroscopy, and
chemical analysis. We failed to precipitate bismuth sal-
icylate with the stoichiometry salicylate : bismuth = 3
from perchloric acid solutions.
When bismuth is precipitated by sodium salicylate
from nitric acid solutions at 70°ë and the mole ratio sal-
icylate : bismuth = 0.5, the free salicylic acid concen-
tration in solution is 0.5 mol/L. The precipitate from
such solutions is dark red, apparently because of partial
nitration of salicylic acid in solution with the formation
of its nitro derivatives [19]. As the mole ratio increases
b
c
0
10
15
2θ, deg
20
25
Fig. 2. X-ray diffraction patterns for (a) bismuth(III)
monosalicylate, (c) bismuth(III) disalicylate, and (b) their
mixture. θ is Bragg’s angle (deg).
bismuth monosalicylate that contains 0.032% nitrate
ions. As the ratio increases to 1.5, the precipitate is a
mixture of bismuth monosalicylate and disalicylate.
When n = 2–6, bismuth precipitates as disalicylate;
pH changes from 1.1 to 4.2. When bismuth is precipi-
tated from hydrochloric acid solutions by addition of
sodium salicylate until the ratio of salicylate ions to bis-
muth in solution becomes 6, X-ray diffraction identifies
the precipitate as bismuth oxochloride BiOCl [20]. In
this case, the sodium salicylate–induced decrease in
hydrogen ion concentration in solution is responsible
further to 1.1, pH increases to 0.9 and the precipitate is for the increased bismuth precipitation percentage.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 6 2009

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TIMAKOVA et al.
‡
‡
b
b
c
c
1600 14001200 1000 800 600 400 200
32003000
–1
ν, cm
3200
2800
2400
1600
1200
800
400
–1
ν, cm
Fig. 3. IR absorption spectra of (a) salicylic acid, (b) bis-
muth(III) monosalicylate, and (c) bismuth(III) disalicylate.
Fig. 4. Raman spectra of (a) salicylic acid, (b) bismuth(III)
monosalicylate, and (c) bismuth(III) disalicylate.
Thus, bismuth monosalicylate for use as a drug sub- rical stretching vibrations of carboxylate groups
ν‡s(ëéé–) appear in the bismuth salicylate spectra as bands
stance can be precipitated from both perchloric and
at 1525 and 1545 cm–1 (IR) for I, 1519 and 1540 cm–1
(Raman) for I, 1510 and 1540 cm–1 (IR) for II, and
1504 and 1540 cm–1 (Raman) for II; symmetrical
stretching vibrations of carboxylato groups νs(ëéé–)
nitric acid solutions (which are usually used to synthe-
size bismuth compounds) when the mole ratio of sali-
cylate ions to bismuth in solution is 1.0 : 1.2.
We found X-ray diffraction data only for bismuth
salicylate Bi2(C6H4OHCOO)3 in Hanawalt et al.’ work
[11]. Comparing the X-ray diffraction patterns of the
precipitation products with various ratios of salicylate
ions to bismuth (1, 1.5, and 2) (Fig. 2), we see that only
two bismuth compounds (monosalicylate and disalicy-
late) can be precipitated from perchloric or nitric acid
solutions. The product of the 1.5 stoichiometry is a
mixture of these two compounds. Our data imply that
bismuth salicylate described by Hanawalt et al. [11] as
Bi2(C6H4OHCOO)3 with characteristic diffraction
peaks (d/n = 2.02, 2.08, 2.26, 2.40, 2.52, 2.75, 3.15,
3.40, 3.98, 4.48, 4.95, 6.20, 6.80, 7.50, 16.0) is actually
a mixture of bismuth monosalicylate and disalicylate.
appear as bands at 1390 cm–1 (IR) for I and 1414 cm–1
(Raman) for I, 1365 cm–1 (IR) for II and 1412 cm–1
(Raman) for II; the bands of the stretching vibrations of
the carbonyl ν(ë=é) at 1660 cm–1 (IR) and 1636 cm–1
(Raman), which appear in the spectra of salicylic acid
[21], disappear from the spectra. For bismuth salicy-
lates, ∆ ν(ëéé–) = ν‡s(ëéé–) – νs(ëéé–) in IR spec-
tra is 135 and 160 cm–1 for I and 145 and 175 cm–1 for II;
these values indicate that the salicylate ligand in com-
pound I is mainly bidentate coordinated and in com-
pound II has bidentate and bidentate-bridging coordi-
nation [23].
The substitution of a bismuth-containing cation for
protons in the carboxylate group of salicylic acid is proven
by the following features of the IR spectra of bismuth sal-
icylates: weak broad bands within 2500–3000 cm–1 asso-
ciated with the stretching mode ν(éç)ëééç, bands of the
Structural features of bismuth monosalicylate (I)
and disalicylate (II) were determined from the analysis
of IR absorption and Raman vibration spectra (Figs. 3, 4).
Characteristic bands in the spectra were assigned with
reference to the spectra of salicylic acid and other metal
salicylates [21, 22]. For example, the substitution of a
bismuth-containing cation for carboxy protons is
out-of-plane bending vibrations δs(éç)ëééç at 892 cm–1,
and those of scissoring vibrations δ(éç)ëééç at
proven by the following spectral features: antisymmet- 1445 cm–1 do not appear; instead, medium-intensity
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PRECIPITATION OF BISMUTH(III) SALICYLATES
877
bands of scissoring vibrations δs(ëéé–) appear at
of monocarboxylates. We found metallic bismuth only
in the products of monosalicylate thermolysis at 300–
400°ë in vacuo. However, metallic bismuth powders
flash in air at ambient temperature, and their surface is
covered by oxide. Noteworthy, the thermal transforma-
tions of bismuth monosalicylate and disalicylate are of
practical value for preparing various bismuth oxide
polymorphs for use in manufacturing bismuth oxide
materials, and these transformations need special and
comprehensive investigation. The thermoanalytical
curves in both cases show that heating ends with bis-
muth oxide formation. The endotherm at 720°ë is due
to the polymorphic transformations of monoclinic
α-Bi2O3 to cubic face-centered high-temperature
860 cm–1 in I and a weak band appears at 875 cm–1 in
II; bands of stretching vibrations ν(Bi–é) appear at
485 cm–1 (IR) for I and II, 365 and 391 cm–1 (Raman)
for I, and 353 and 389 cm–1 (Raman) for II [24]; and
strong bands of the bending vibrations δ(Bi–O) appear
at 163 cm–1 (Raman) for I and 154 cm–1 (Raman) for
II [25].
The existence of undissociated phenolic groups in
coordinated salicylate anions is proven by the appear-
ance of the stretching vibrations ν(ë–é) of the phenol
group at 1250 cm–1 (IR), 1237 and 1250 cm–1 (Raman)
for I, 1250 cm–1 (Raman) for II; the in-plain bending
vibrations δ(ëé–ç) at 1345 cm–1 (IR), 1389 cm–1 δ-Bi2O3 (730°ë) [26]. The latter is stable until the oxide
(Raman) for I, and 1390 cm–1 (Raman) for II in the melts (at 825°ë) [26]; the relevant endotherm has a
spectra of bismuth salicylates. If the phenol hydroxide peak 810°ë. The calculated weight loss for the thermol-
group were coordinated to the bismuth-containing cation ysis of BiOC7H5O3 and Bi2O(C7H5O3)4 to Bi2O3 agrees
via the oxygen atom, the stretching vibrations ν(ë–é)
have shifted to lower frequencies [18].
with the found value: 71.3 mg (calcd., 71.6 mg) and
104.4 mg (calcd., 105.1 mg), respectively.
The IR spectra of bismuth salicylates in the region
2950–3350 cm–1 feature broad absorption bands with
peaks at 3060 cm–1 (for I and II), which are associated
with the in-ring stretching vibrations ν(ëç), and peaks
at 3200 cm–1 (I) and 3180 cm–1 (II) with a shoulder at
3260 cm–1 (II); the last peaks are associated with the
stretching vibrations of phenolic groups, which are
involved in the system of hydrogen bonds.
Electron micrographs show that bismuth monosali-
cylate samples precipitated by salicylic acid from per-
chloric acid solutions at 70°ë (pH 0.9) are needle-
shaped crystals (Fig. 6a) 10–20 µm long and 0.2 µm
thick. As pH increases to 1.6, the product consists of
needle-shaped crystals with sizes up to 1 µm; these
crystals are piled into loose agglomerates up to 5 µm in
size (Fig. 6b). Precipitation from nitric acid solutions
with pH of 0.9–3 at 70°C yields bismuth monosalicy-
late in the form of needles 1–5 µm long and about
0.2 µm thick (Fig. 6c). The Ural Chemicals Plant pro-
duces bismuth monosalicylate as elongated crystals
10–30 µm long and 0.2–2 µm thick (Fig. 6d). The bis-
muth disalicylate samples (70°C, pH 0.9) precipitated
from either perchloric or nitric acid solutions are elon-
gated prismatic crystals with basis planes of 10–50 µm
and thicknesses of 3–5 µm (Figs. 6e, 6f).
From the examination of the IR and Raman spectra
of bismuth salicylates and chemical analysis data, we
infer that the bismuth-containing cations in our pre-
pared compounds are bound to salicylate ligands
through carboxy groups; the bismuth-containing cat-
ions are not directly coordinated to phenolic hydroxy
groups. Our results imply that bismuth monosalicylate
(I) and bismuth disalicylate (II) are formulated as
BiOC7H5O3 and Bi2O(C7H5O3)4, respectively.
Our experiments also show that the specific surface
area of bismuth monosalicylate depends on pH and
temperature. For example, for bismuth monosalicylate
precipitated from perchloric acid solutions at 70°C and
pH 0.9 and 1.6, the specific surface area is 6.2 and
20.7 m2/g, respectively; at 25°C and pH 0.9, the spe-
cific surface area is 12.8 m2/g. Upon precipitation from
nitric acid solutions at pH 2.0 and 50, 70, or 90°C, the
specific surface area of bismuth monosalicylate is 9.9,
9.3, or 6.3 m2/g, respectively. Bismuth monosalicylate
produced by the Ural Chemicals Plant (Specification
TU 6-09-02-55-88) has a specific surface area of
0.80 m2/g. For bismuth disalicylate precipitated at 70°C
from perchloric or nitric acid solution, the specific sur-
face area is 0.25 and 0.20 m2/g, respectively.
DTA and thermogravimetry (TG and DTG) for bis-
muth salicylate samples (Figs. 5a, 5b) in air indicate the
occurrence of a series of consecutive endothermic and
exothermic stages and the possibility of preparing bis-
muth oxides by thermolysis of its salicylates. Bismuth
monosalicylate thermolysis starts with melting (endot-
herm at 280°ë) and then involves the decomposition of
salicylate ions (exotherm at 400°ë) and the formation
of bismuth oxide. The thermoanalytical curves for bis-
muth disalicylate have a more complex trend; endot-
herms appear at 180, 250, and 340°ë and an exotherm
appears at 400°ë. According to X-ray diffraction data
[20], bismuth monosalicylate thermolysis for 6 h at
300°ë yields bismuth oxide as tetragonal β-Bi2O3,
which transforms to monoclinic α-Bi2O3 at 350°ë and
above. We have not observed metallic bismuth,
Thus, bismuth is precipitated by sodium salicylate
although it is usually formed as a result of thermolysis from perchloric acid solutions as monosalicylate
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 6 2009

878
TIMAKOVA et al.
í
Exo
∆T
(a)
810
DTG
720
Endo
DTA
TG
400
280
∆m, mg
0
20
40
60
T, °C
80
í
(b)
Exo
810
DTG
∆T
720
Endo
DTA
400
340
250
180
T, °C
∆m, mg
TG
0
20
40
60
80
100
120
Time
Fig. 5. Thermoanalytical curves for (a) bismuth(III) monosalicylate and (b) bismuth(III) disalicylate samples in air. Sample size:
200 mg.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 6 2009

PRECIPITATION OF BISMUTH(III) SALICYLATES
879
1 µm
1 µm
(‡)
(b)
1 µm
10 µm
(c)
(d)
10 µm
10 µm
(e)
(f)
Fig. 6. Micrographs of (a–d) bismuth(III) monosalicylate and (e, f) bismuth(III) disalicylate precipitated from (a, b, e) perchloric
acid and (c, f) nitric acid solutions at 70°C and pH of (a, b, e, f) 0.9 and (c) 1.6. (d) Micrograph of a commercially available sample.
BiOC7H5O3, and from nitric acid solutions, both as from nitric acid solutions with mole ratios of salicylate
ions to bismuth of 1.0–1.2, pH of 1–3, and temperature
of 50–90°ë. When mole ratios of salicylate ions to bis-
muth exceed 1.5, precipitates contain a bismuth disali-
cylate impurity; when the mole ratio is 3.0 or higher,
monosalicylate and disalicylate Bi2O(C7H5O3)4. In cases
where salicylic acid is added to perchloric acid solu-
tions, bismuth precipitates as monosalicylate or disali-
cylate, depending on the salicylate ion concentration. It
is pertinent to prepare bismuth(III) monosalicylate bismuth disalicylate precipitates as an individual com-
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TIMAKOVA et al.
13. Yu. M. Yukhin and Yu. I. Mikhailov, Chemistry of Bis-
muth Compounds and Materials (Sib. Otd. Ross. Akad.
Nauk, Novosibirsk, 2001) [in Russian].
14. P. P. Korostylev, Photometric and Complexometric Anal-
ysis in Metallurgy. Spravochnik, Ed. By A. I. Busev
(Metallurgiya, Moscow, 1984) [in Russian].
pound. We have shown that the synthesis parameters
considerably affect the morphology and specific sur-
face area of the products.
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RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 6 2009