Precipitation of Bismuth(III) Tartrates from Nitrate Solutions

Article abstract of DOI:10.1023/A:1023376526485

The precipitation of bismuth(III) from nitrate solutions on addition of aqueous solutions of tartaric acid and sodium tartrate was studied by X-ray phase analysis, thermogravimetry, IR spectroscopy, and chemical analysis. Conditions for the formation of [

Full text of DOI:10.1023/A:1023376526485

Russian Journal of Applied Chemistry, Vol. 76, No. 1, 2003, pp. 1 6. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 1,
003, pp. 3 8.
Original Russian Text Copyright
2
2003 by Logutenko, Evseenko, Yukhin, Afonina.
INORGANIC SYNTHESIS
AND INDUSTRIAL INORGANIC CHEMISTRY
Precipitation of Bismuth(III) Tartrates from Nitrate Solutions
O. A. Logutenko, V. I. Evseenko, Yu. M. Yukhin, and L. I. Afonina
Institute of Chemistry of Solids and Mechanochemistry, Siberian Division, Russian Academy of Sciences,
Novosibirsk, Russia
Received September 16, 2003
Abstract The precipitation of bismuth(III) from nitrate solutions on addition of aqueous solutions of tartaric
acid and sodium tartrate was studied by X-ray phase analysis, thermogravimetry, IR spectroscopy, and
chemical analysis. Conditions for the formation of [Bi(NO )(H O) ]C H O and [Bi(C H O )(C H O )]
3
2
3
4
4
6
4
4
6
4 5 6
3
H O were determined.
2
Bismuth(III) compounds with tartaric acid and its
salts are widely used in medicine for treatment of
various diseases and also in the synthesis of bismuth-
containing oxide materials [1, 2]. Usually they are
prepared by precipitation of bismuth(III) from nitrate
solutions with tartaric acid or its alkali metal salts [3].
As the composition ot the precipitated products is
sensitive to the synthesis conditions [pH of the medi-
um, ratio of tartrate ions and bismuth(III) in the aque-
ous phase, temperature, etc.], and tartaric acid itself
has several donor centers and four labile protons,
compounds of various compositions can be formed in
these systems. It was shown that bismuth(III) can
form the following compounds with tartrate ions:
BiC H O nH O [3, 4], Bi(OH) Bi(OH)(C H O )
Precipitation of Bi(III) was carried out by adding
aqueous solutions of sodium tartrate C H O Na or
4
4
6
2
tartaric acid C H O to a solution of Bi(NO ) con-
4
6
6
3 3
1
taining (g l ): Bi(III) 440 and free nitric acid 74.
The solution of Bi(NO ) was prepared by dissolving
3
3
Vi 00 grade metallic bismuth (no less than 99.98% Bi)
in 9 M HNO ; its composition corresponded to solu-
3
tions usually used in the technology of bismuth(III)
compounds. The volume ratio of the initial and final
bismuth-containing solutions was 1 : 10; it was ad-
justed by adding distilled water. The experiments
were carried out in fluoroplastic vessels equipped with
stirrers. The mixture was stirred for 2 h. After sedi-
mentation for 1 h, the precipitate was filtered off,
washed on the filter with distilled water, and dried in
air. The X-ray phase analysis of the precipitated prod-
ucts was carried out on a DRON-3 diffractometer us-
ing CuK radiation (rotation rate of the counter
4
5
7
2
2
4 3 6
[
5], and Bi(C H O )(C H O ) 3H O [4, 6]. Reac-
4 4 6 4 5 6 2
tions of these compounds with solutions of ammonia
and of alkali metal hydroxides and acetates yield
three-component complex compounds, both insoluble,
1
0.5 deg min , I = 1000). The DTA and TG curves for
+
+
+
+
e.g., C H O BiM (M = K , Na , Li , NH ) [3],
the samples under study were taken on an MOM deri-
4
3
6 2
6
4
1
[
Bi(C H O ) ]NH nH O [7], and soluble in water,
vatograph (Hungary) at a heating rate of 10 deg min .
4
4
4
2
The IR absorption spectra in the range 400 4000 cm 1
were recorded on a Specord IR-75 spectrophotometer.
Samples were prepared in the form of pellets with cal-
cined KBr. The electron micrographs of products were
taken on a JSMT-20 scanning microscope with a
e.g., C H O BiNa [3], Na(BiO) C H O and
Na(BiO) C H O [8], Bi(HC H O ) , and [Bi(OH)
4
4
7
2 4 3 6
3
4
2
6
4
4
6 4
3
2
C H O ] [9].
4
4 6
Bismuth(III) compounds are usually synthesized by
hydrolytic processing of nitrate solutions obtained by
2
00 resolution. The specific surface area of the sam-
dissolution of metallic bismuth in HNO . Therefore, it
3
ples was measured by thermal desorption of argon,
monitored chromatographically. Macroamounts of
Bi(III) in the liquid and solid phases were determined
by EDTA titration using xylenol orange as indicator,
and its microamounts were determined photocolori-
merically in the presence of KI. The concentrations of
metal ions (Bi, Pb, Ag, Cu, Fe, Zn) were determined
by the atomic absorption method on a Saturn 2M
spectrophotometer. The precipitated products were
is of practical interest to study the precipitation of
Bi(III) tartrate from nitrate solutions of the composi-
tion similar to that of the process solutions.
In this work, we studied how the concentration
of tartrate ions, temperature, and pH affect the degree
of Bi(III) precipitation from nitrate solutions, and
also the composition and purity of the precipitated
products.
1
070-4272/03/7601-0001$25.00 2003 MAIK Nauka/Interperiodica

2
LOGUTENKO et al.
correspond to any of the known bismuth compounds.
R, %
However, according to the chemical analysis, the
samples contain (%) Bi 49.00, C 9.74, H 1.42, and
N 2.46; the molar ratio of Bi(III) and tartrate and ni-
trate ions in the precipitate is 1 : 1.1 : 1.2, which
suggests that, under these conditions, a compound of
the composition [Bi(NO )(H O) ]C H O mainly
3
2
3
4 4 6
precipitates. The possibility for its formation was
reported in [12].
The precipitates obtained at 23 C and n no less
than 2 and also at 60 C and n no less than 3 consist
of a compound with the composition [Bi(C H O )
4
4 6
Fig. 1. Degree of Bi(III) precipitation R as a function of the
molar ratio n of tartrate ions to Bi(III) in solution. Agents
added to a bismuth-containing solution: (1, 2) tartaric acid
and (3, 4) sodium tartrate. Temperature, C: (1, 3) 23 and
(
C H O )] 3H O, which contains two different tar-
4 5 6 2
2
trate ligands, (+)-tartrate and (+)-tartrate . This is
confirmed by the X-ray phase and chemical analyses.
The diffraction peaks characteristic of this compound
(
2, 4) 60.
(d/n 1.84, 2.15, 2.46, 3.31, 4.36, 6.74, and 9.08 ) [6]
preliminarily dissolved in HNO (1 : 1). The concen-
are present in the X-ray pattern (Fig. 2, curve 4), and
the molar ratio of Bi(III) and tartrate ions in the pre-
cipitate is 1 : 2 (the product contains 37.00% Bi,
17.61% C, and 2.64% H). The orthorhombic crystal
structure of this compound (space group P2 2 2 ) in-
3
tration of nitrate ions was determined photometrically
with sodium salicylate after dissolution of the precipi-
tates by treatment with a sodium hydroxide solution
(2 M) at 70 90 C.
1
1 1
cludes a three-dimensional network with bridging and
chelating bonds of polydentate hydroxocarboxylate
ligands, and the coordination number of Bi(III) is
The study of the influence of the tartaric acid con-
centration on the degree of bismuth precipitation R
Fig. 1, curves 1 and 2) shows that, as the concentra-
(
4
[6].
tion of tartrate ions in solution increases, the degree
of bismuth(III) precipitation at 23 1 C first slightly
decreases, passes through a minimum at the molar
ratio of tartrate ions and Bi in solution n equal to 0.5,
and then increases, reaching 98.8% at n = 5. Increased
process temperature results in decreased degree of
Bi(III) precipitation. The degree of Bi(III) precipita-
tion at 60 1 C remains constant and independent of
tartaric acid concentration up to n = 3, and at higher
n the degree of precipitation grows, reaching 91.1%
at n = 5.
The thermal (DTA, TG, DTG) analysis of Bi(III)
oxohydroxonitrates and tartrates in air reveals a num-
ber of endo- and exothermic stages, demonstrating
the possibility of obtaining -Bi O by thermal de-
2
3
composition of Bi(III) tartrates. Comparison of the
thermograms of the samples obtained by Bi(III) pre-
cipitation from nitrate solutions in the absence of
tartaric acid (Fig. 3a) and at n equal to 1 (Fig. 3b) and
5 (Fig. 3c) shows that the total weight loss increases
with increasing n. This is due to an increase in the
content of tartrate ions in the precipitated products.
The thermal analysis of bismuth(III) oxohydroxoni-
trate reveals stepwise dehydration, dehydroxylation,
and decomposition of nitrate with the formation of
According to the X-ray analysis (Fig. 2), the basic
nitrates [Bi O (OH) ](NO ) 4H O (23 C) and [Bi
6
4
3 6
4
2
3 6
2
6
O (OH) ](NO ) H O (60 C) are formed in the sys-
4
4
tem in the absence of tartrate ions. The X-ray patterns
of these compounds (Fig. 2, curves 1, 2) contain the
characteristic diffraction peaks: d/n 1.68, 2.11, 2.39,
Bi O [13]. The thermal decomposition of Bi(III)
2
3
nitratotartrate starts from water removal (endothermic
effect at 100 C) and decomposition of nitrate and tar-
trate ions (exothermic effects at 130, 240, and 320 C).
Bismuth(III) tartrate trihydrate obtained at n = 5 loses
weight in two stages: first water is removed (endo-
thermic effect at 140 C), and then tartrate ions de-
compose with endothermic effects at 270 and 340 C.
It is seen from the thermograms that heating of all the
samples gives Bi O as the final product. The endo-
2
.77, 2.82, 3.30, 3.81, and 8.42 for the tetrahydrate
and 1.51, 1.73, 2.17, 2.50, 2.84, 3.75, 4.31, and
.37 for the monohydrate [10, 11]. The precipitates
obtained at the initial molar ratio of tartrate ions and
bismuth in solution less than 1 are X-ray amorphous;
in this case, Bi(III) seems to be precipitated as a mix-
ture of oxohydroxonitrate and nitratotartrate. At n
equal to 1, diffraction peaks with d/n 2.24, 3.72, 5.57,
and 10.92 are clearly seen in the X-ray patterns of
the precipitates (Fig. 2, curve 3). This pattern does not
7
2
3
thermic effect at 730 C is due to the polymorphous
transition of -Bi O into the high-temperature modi-
2
3
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 1 2003

PRECIPITATION OF BISMUTH(III) TARTRATES FROM NITRATE SOLUTIONS
3
(
a)
DTG
DTA
,
mg
TG
(
b)
DTG
DTA
,
mg
TG
(
c)
DTG
DTA
,
mg
TG
,
deg
Fig. 2. Diffraction patterns of Bi(III) precipitates obtained
from nitrate solutions by adding (1, 2) water and (3, 4) tar-
taric acid. (I) Signal intensity and ( ) Bragg angle. n:
Fig. 3. Thermograms of Bi(III) precipitates obtained from
nitrate solutions by adding (a) water and (b, c) tartaric
acid. 23 C; sample weight 200 mg. ( m) Weight loss and
( ) time. n: (a) 0, (b) 1, and (c) 5.
(
(
1, 2) 0, (3) 1, and (4) 5. Temperature, C: (1) 23 and
2 4) 60.
fication -Bi O , and the endothermic effect at 820 C
of 0.073, 0.34, 0.41, 0.61, 1.03, and 1.33 M the con-
centration of Bi(III) in solution is 20.9, 2.6, 1.0, 2.1,
11.5, and 12.8 g l , respectively, i.e., the maximal
2
3
is due to melting of Bi O [14]. To transform Bi(III)
2
3
1
oxohydroxonitrate into the oxide, it is necessary to
calcine it at a temperature of no less than 540 20 C,
whereas Bi(III) tartrates can be transformed into the
oxide by their thermal decomposition at 320 20 C.
degree of Bi(III) precipitation (97.5%) is reached at
the 0.4 0.5 M concentration of hydrogen ions. The
concentration of free nitric acid in precipitation of
bismuth ditartrate by adding tartaric acid to a solution
of Bi(NO ) is 0.75 M. To achieve the maximal pre-
The study of the effect exerted by pH of the medi-
um on the degree of Bi(III) precipitation has shown
that, at the molar ratio of tartrate ions and Bi(III)
3
3
cipitation, it is necessary to neutralize the solution by
adding NaOH or NH H O. However, the degree of
3
2
+
equal to 2.1, 23 C, and the concentration of H ions
Bi(III) precipitation sharply decreases at the concen-
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 1 2003

4
LOGUTENKO et al.
salt. The carboxy groups in the IR spectrum of tartaric
acid (Fig. 4, curve 1) give a broad band in the range
300 2500 cm 1 corresponding to O H stretching
A
3
vibrations of carboxy groups bound in dimers. A band
with a maximum at 1720 cm 1 corresponds to stretch-
ing vibrations of the C=O bonds of free carboxy
groups. A band with well-defined maxima at 3320 and
3
400 cm 1 corresponds to stretching vibrations of
hydroxy groups involved to various extents in the
hydrogen bonding.
The IR spectrum of sodium tartrate C H O Na
2
4
4
6
(
Fig. 4, curve 2) contains bands of the COO group
with C O bonds of the order 1.5 at 1610 (asymmetric
stretching vibrations) and 1410 cm 1 (symmetric
stretching vibrations), indicating the transformation of
the carboxy groups to the anionic form. A broad band
with several maxima in the range 3560 3200 cm 1
corresponds to hydroxy groups involved in various
hydrogen bonds and to molecular water present in
a certain amount in the associated form.
,
cm 1
A similar IR pattern is observed with the compound
Fig. 4. IR absorption spectra of (1) tartaric acid, (2) sodium
tartrate, (3) [Bi(NO )(H O) ]C H O , and (4) [Bi(C H O )
[
Bi(NO )(H O) ]C H O obtained at the 1 : 1 molar
3 2 3 4 4 6
3
2
3
4
4
6
4 4 6
(
C H O )] 3H O. (A) Absorption and ( ) wave number.
ratio of tartrate ions and Bi(III) (Fig. 4, curve 3).
4
5
6
2
However, along with the absorption bands of the de-
1
tration of free HNO in solution less than 0.3 M,
which may be due to formation of soluble tartrate-
containing complexes. As the concentration of free
protonated carboxy group (1590 and 1390 cm ),
3
1
broadened bands in the range 1400 1280 cm and
a pronounced shoulder at 1310 cm 1 are observed in
the spectrum, which most likely originate from the
absorption of nitrate ions. A broad band with a pro-
nounced maximum at 3400 cm 1 is due to the O H
stretching vibrations of water molecules and hydroxy
groups of tartrate ions involved in hydrogen bonding.
HNO in solution increases over 0.6 M, the degree of
3
Bi(III) precipitation as a dihydrate also decreases, and
+
at 1.33 M H it is as low as 70.9%.
The degree of Bi(III) precipitation as a function of
the concentration of sodium tartrate is plotted in
Fig. 1 (curves 3, 4), which shows that this degree first
increases, passes through a maximum at the molar
ratio of tartrate ions and Bi(III) of 1.6 (R = 98%), and
then sharply decreases, i.e., the precipitate dissolves.
Such a pattern is due to the capability of Bi(III) to
form water-soluble complexes with tartrate ions. The
increase in the sodium tartrate concentration initially
results in the precipitation of basic Bi(III) nitrates and
tartrates of various compositions. The chemical analy-
sis has shown that the products precipitated at n 1
and 2 contain, respectively (%): Bi 49.7, Na 1.43,
NO 11.32 and Bi 35.0, Na 6.1 and NO 17.13. The
Similar to the spectrum of tartaric acid, the IR
spectrum of bismuth ditartrate (Fig. 4, curve 4) con-
tains, along with the absorption bands of carboxylate
1
groups (1590 and 1390 cm ), also the bands of
carboxy groups: a broad band in the range 3200
1
2
400 cm , which corresponds to the stretching vibra-
tions of OH groups of carboxylic acids involved in
hydrogen bonding, and a band at 1720 cm 1 of the
stretching vibrations of the C=O bond in the carboxy
group. This spectral pattern is quite consistent with
the composition [Bi(C H O )(C H O )] 3H O.
4
4
6
4
5
6
2
3
3
The electron micrographs (Fig. 5a) show that
Bi(III) nitratotartrates obtained at 23 and 60 C consist
of relatively large aggregates of the size from 3 to
sodium bismuth(III) molar ratio in the precipitate is
.25 and 1.5, respectively. At n > 2 (23 C) and n > 3
60 C), the degree of Bi(III) precipitation sharply de-
0
(
40 m, with signs of a block structure. The aggregates
creases, which is due to formation of water-soluble
Bi(HC H O ) complex ions [9].
consist of smaller crystals. Bismuth(III) ditartrate tri-
hydrate obtained at 23 C consists of oriented inter-
grown pieces of elongated prismatic (almost needle-
like) crystals of the size of about 3 10 m, whereas
4
4 6 4
The IR absorption spectra of bismuth(III) tartrates
were compared to those of tartaric acid and its sodium
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 1 2003

PRECIPITATION OF BISMUTH(III) TARTRATES FROM NITRATE SOLUTIONS
crystals of the product obtained at an elevated tem-
5
(
a)
perature (60 C) have a size of 20 60 m (Fig. 5c).
When Bi(III) is precipitated from nitrate solutions
by adding a sodium tartrate solution, an X-ray amor-
phous product is obtained; its aggregates, having a
size of 1 5 m, consist of submicrometer X-ray
amorphous particles (Fig. 5d). The specific surface
areas of sodium tartrates obtained at 23 and 60 C are,
respectively, for the nitratotartrate 0.8 and 0.7, for the
ditartrate 0.6 and 0.4, and for the sodium-containing
5
0 m
2
1
tartrate 1.5 and 1.1 m g , i.e., the specific surface
area of Bi(III) tartrates decreases with increasing
temperature.
(b)
Bismuth(III) compounds are usually synthesized
from nitrate solutions starting from Vi-1 grade bis-
muth which contains Ag and Pb as the main impuri-
ties. The Bi(III) tartrate [Bi(C H O )(C H O )]
4
4
6
4 5 6
3
H O was precipitated by adding tartaric acid to a
2
50 m
solution of Bi(NO ) at 23 1 C and the 5 : 1 ratio of
3
3
tartrate ions to Bi(III) in solution. Enlarged tests were
carried out with a Bi(III)-containing solution, which
was obtained by dissolving Vi-1 grade bismuth con-
taining 0.06 wt % Ag and 1.2 wt % Pb. The mixture
was stirred for 2 h and settled. The mother solution
containing 0.69 g l 1 of Bi(III) was separated by
decanting. The precipitate of Bi(III) tartrate was
washed with one portion of a nitrate solution with
pH 1.0 and two portions of distilled water. The result-
ing Bi(III) tartrate contained (wt %) Pb 0.55, Ag 1.5
(
c)
5
0 m
4
4
3
4
1
0 , Cu 2.5 10 , Fe 1.0 10 , and Zn 2.5 10 ,
(
d)
i.e., the removal of Pb(II) from Bi(III) was inefficient.
Therefore, to synthesize high-purity Bi(III) tar-
trate, it is necessary to use the Vi 00 grade metal
(
99.98% Bi) or to preliminarily remove impurity
metal ions by precipitating Bi(III) from nitrate solu-
tions as its oxohydroxonitrate [15]. To remove im-
purity metal ions from Bi(III), we diluted the initial
nitrate solution by a factor of 2 with distilled water
and added a 2.5 M solution of (NH ) CO with stir-
50 m
4
2
3
1
ring to the solution containing 220 g l of Bi(III) and
Fig. 5. Electron micrographs of (a) nitratotartrate, (b) ditar-
trate, and (c) sodium-containing tartrate of Bi(III) obtained
on adding (a c) tartaric acid and (d) sodium tartrate to
3
0
7 g l 1 of free HNO , until pH of the pulp became
.9. The precipitate was washed with two portions of
3
a solution of Bi(NO ) . Temperature ( C): (a, b, d) 23 and
distilled water, and the resulting oxohydroxonitrate
Bi O (OH) ](NO ) 3H O was dissolved in 6.0 M
3 3
(
c) 60.
[
6
5
3
3 5
2
HNO . The precipitation of Bi(III) ditartrate trihydrate
3
CONCLUSIONS
by adding tartaric acid to the resulting solution under
the above-mentioned conditions gave a product con-
(
1) It is appropriate to synthesize the Bi(III) ditar-
4
6
6
taining (wt %) Pb 5.0 10 ; Ag 3 10 ; Cu 2 10 ;
trate [Bi(C H O )(C H O )] 3H O by its precipita-
4
4
6
4
5
6
2
4
5
Fe 1.0 10 ; Zn 8 10 ; and Ca, Mg, and Na
tion from bismuth-containing nitrate solutions by ad-
ding tartaric acid at the molar ratio of tartrate ions and
4
<
1.0 10 .
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 1 2003

6
LOGUTENKO et al.
+
Bi(III) in solution no less than 2, H concentration
of 0.4 0.5 M, and temperature of 22 3 C.
5. Kirchhoff, G.A., Spektr, M.O., and Akon’yants, E.A.,
Khim.-Farm. Prom st., 1933, no. 3, pp. 122 123.
6
. Herrmann, W.A., Herdtweck, E., Scherer, W., et al.,
Chem. Ber., 1993, vol. 126, pp. 51 56.
(
2) When synthesizing high-purity Bi(III) ditar-
trate, it is necessary to use high-purity Bi(III), or, if
using technical-grade Bi(III), to preliminarily perform
hydrolytic purification of bismuth by its precipitation
as oxohydroxonitrate.
7. Sagatys, D.S., O’Reily, E.J., Patel, S., et al., Aust. J.
Chem., 1992, vol. 45, pp. 1027 1034.
8. Tsimbler, M.E., Ukr. Khim. Zh., 1952, vol. 18,
pp. 376 380.
(
3) Bi(III) is precipitated as the nitrotriaquatartrate
9
. Tikhonov, A.S., Zh. Obshch. Khim., 1954, vol. 24,
no. 1, pp. 37 41.
[
1
Bi(NO )(H O) ]C H O from a solution with the
: 1 molar ratio of tartrate ions and Bi(III), whereas
3
2
3
4 4 6
the precititation with sodium tartrate gives sodium-
containing tartrates.
10. Lazarini, F., Cryst. Struct. Commun., 1979, vol. 8,
pp. 69 74.
1
1
1
1. Afonina, L.I., Yukhin, Yu.M., and Vorsina, I.A., Sib.
Khim. Zh., 1993, no. 3, pp. 13 19.
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