Synthesis and thermal decomposition of [Bi6O4(OH)4](NH2SO3)6

Article abstract of DOI:10.1016/j.tca.2010.01.026

The interaction of Bi(III) with aqueous solution of sulfamic acid is investigated, and a new compound with the following composition [Bi₆O₄(OH)₄](NH₂SO₃)₆ is derived. The substance obtained is characterized by various methods: elemental analysis, DTA, TG, FTIR and X-ray diffraction. Based on the experimental results, a mechanism of thermal decomposition of the newly synthesized compound is proposed.

Full text of DOI:10.1016/j.tca.2010.01.026

Thermochimica Acta 502 (2010) 90–93
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Short communication
Synthesis and thermal decomposition of [Bi O (OH) ](NH SO )
3 6
6
4
4
2
a,∗
b
c
A. Zahariev , V. Parvanova , N. Kaloyanov
a
Department of Chemistry, Technical University, 8 St. Kliment Ohridski Blvd., 1000 Sofia, Bulgaria
Department of General and Inorganic Chemistry, University of Chemical Technology and Metallurgy, 8 St. Kliment Ohridski Blvd., 1756 Sofia, Bulgaria
Department of Organic Chemistry, University of Chemical Technology and Metallurgy, 8 St. Kliment Ohridski Blvd., 1756 Sofia, Bulgaria
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
The interaction of Bi(III) with aqueous solution of sulfamic acid is investigated, and a new compound with
the following composition [Bi6O4(OH)4](NH2SO3)6 is derived. The substance obtained is characterized
by various methods: elemental analysis, DTA, TG, FTIR and X-ray diffraction. Based on the experimental
results, a mechanism of thermal decomposition of the newly synthesized compound is proposed.
Received 17 November 2009
Received in revised form 26 January 2010
Accepted 31 January 2010
Available online 10 February 2010
©
2010 Elsevier B.V. All rights reserved.
Keywords:
Bi(III) complexes
Thermal decomposition
X-ray diffraction
DTA–TG
1
. Introduction
them the crystalline structure has been ascertained. There is also a
plenty of complexes with anions of gallic, malonic, lactic, nitrilo-
triacetic and ethylenediaminetetraacetic acids depicted [11–13].
Recently, data about the synthesis of Bi(III)-stearate and Bi(III)-
oxidohydroxidolaurate have been reported [14,15].
However, data about the interaction between Bi(III) and sul-
famic acid are not found in the literature. Therefore, it is of great
interest to investigate this interaction and to characterize the
product obtained in view of its potential implementation as a bio-
logically active substance.
The synthesis and characterization of Bi(III) compounds with
various inorganic and organic anionic species is a subject of thor-
ough investigations [1]. There are a small number of water soluble
inorganic salts of Bi(III) derived by interaction of Bi(III) with
strong-acid anions (e.g. nitrate, sulfate, and perchlorate). How-
ever, in a weak acidic and alkaline environment they hydrolyze
to a series of poorly soluble compounds because of the formation
(
10−x)+
of polycations of composition [Bi Ox(OH)
solution’s pH [2]. Within pH 1.0–1.2, a species having composition
]
depending on
6
8−x
6
+
[
Bi O (OH) ] is generated [2–5]. Therefore, determining the com-
6 4 4
2. Experimental
position and investigating the properties of Bi(III) salts in aqueous
solutions are oftentimes accompanied by serious difficulties.
Despite the peculiarities mentioned about complicated Bi(III)
pH dependent behaviour, a series of its complexes with various
ligands have been synthesized and characterized. Most impor-
tant of them are the complexes with hydroxidocarboxylic and
aminocarboxylic acids. In the recent years, the interest to the syn-
thesis of Bi(III) compounds containing various acidic anions raised
significantly due to the implementation of a variety of these com-
pounds in the production of antibacterial medicines [1]. A lot of
these compounds contain variable number of water molecules,
The interaction of Bi(III) with sulfamic acid was performed as
3
follows: 40 g Bi(NO ) ·5H O (Merck, p.a.) were added to 170 cm
3
3
2
1
2% (pH 1.0–1.2) aqueous solution of HNH SO (Fluka puriss. p.a.)
2 3
The experimental conditions included 96 h of stirring at room
−
temperature because of the substantial hydrolysis of NH SO3
2
at higher temperatures [16]. The white precipitate obtained was
firstly washed with mother water, then with double distilled water
up to pH 7.0, and finally dried in a desiccator over P O10. The
4
product’s composition was determined by elemental analysis on
VarioELV5.18.018 (Elementar Analysensysteme GmbH, Hannau,
Germany) performing in CHNS mode. The data presented, indicated
by the symbols of the elements, are within ± 0.40% of the theoretical
values:
and many double hydrates containing Na , K and NH4+ have
been synthesized as well. The tartaric- [6–8] and citric acid [9,10]
complexes have been most widely investigated, and for many of
+
+
∗ Corresponding author.
E-mail address: alexs zahariev@yahoo.com (A. Zahariev).
Calcd. %: N – 4.28; S – 9.78; H – 0.81;
Found %: N – 4.30; S – 9.44; H – 1.03.
0
040-6031/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.tca.2010.01.026

A. Zahariev et al. / Thermochimica Acta 502 (2010) 90–93
91
Fig. 2. X-ray diffraction pattern of [Bi6O4(OH)4](NH2SO3)6.
Fig. 1. FTIR spectrum of [Bi6O4(OH)4](NH2SO3)6.
mediate phases formed at different temperatures. The results of
these supporting investigations are summarized in Figs. 4 and 5.
Infrared spectra were recorded on a Perkin-Elmer 1600 Series
−
1
FTIR spectrophotometer in the range of 4400–450 cm , resolution
◦
Considering Fig. 3, a clearly outlined exothermic peak at 230 C
−
1
4
cm in KBr pellets.
appears, and at the same time no mass loss is observed at this tem-
DTA–TG measurements were performed on Derivatograph Q-
◦
perature. In Fig. 4a, FTIR spectrum of the phase at 240 C reveals a
◦
◦
−1
1
500-D (MOM, Hungary), within 20–1000 C and 10 C min rate
−1
−1
decrease in the intensity of vibrations at 1553 cm and 792 cm ,
in air, using Al O as an inert substance. The sample mass used was
2
3
compared to those of the initial substance (Fig. 1). Furthermore, a
5
00 mg.
−1
new absorption band at 1402 cm could be discerned. In Fig. 1,
The final product and intermediate phases after DTA–TG anal-
−1
four absorption bands within 1050–1170 cm appear due to the
◦
ysis (at 240, 320, 440 and 620 C) were characterized by X-ray
stretching vibrations of the S O and S–O bonds in SO . The bands’
3
diffraction (XRD) on automated Siemens D 500 apparatus with
description gives reason to assume that [Bi O (OH) ](NH SO )
6
4
4
2
3 6
◦
4
0 kV Cu K␣ radiation within 2ꢀ = 3–70 .
is generally well crystallized. Taking into consideration the data
from DTA–TG and FTIR, one can conclude that with the increas-
◦
3
. Results and discussion
ing the temperature up to 230 C, a polymorphic re-crystallization
most probably proceeds, and as a result, a thermodynamically more
stable phase is formed. On the other hand, partial transformation
In Fig. 1, the FTIR spectrum of [Bi O (OH) ](NH SO ) is pre-
6
4
4
2
3 6
sented. It is obvious that the most characteristic bands of the
sulfamic acid [17] could be found within the spectrum of the com-
pound synthesized. Its absorption bands, referred to the most likely
vibrations of different functional groups, are given in Table 1.
Within the spectrum under consideration, a broad medium band
−1
at 792 cm appears as well, assigned most probably to bending
vibration of the bridging oxygen atom in Bi–O–Bi species [18].
The X-ray diffraction pattern of the compound under investi-
gation is shown in Fig. 2. It is clearly seen from the figure that a
high-level crystalline phase appears.
In Fig. 3 the results from DTA–TG analyses of new compound
◦
within the range 20–1000 C are presented. Both FTIR and XRD
analyses are also used in the investigation of the DTA–TG inter-
Table 1
FTIR spectral data and band assignments of
[Bi6O4(OH)4](NH2SO3)6.
FTIR, cm 1
−
Assignment
3
3
1
1
1
441 s
␯as NH2
212 sh
629 w
553 w br
226 s
␯s OH + ␯s NH2
␦ S–OH (scissoring)
␦ NH2
␦ OH
1
1
164 s
095 m
␻
NH2 + ␯ S O
1041 vs
r NH2 + ␯ S–O
792 m br
Bi–O–Bi
6
5
10 m
70 s
␦
SO2 (scissoring)
546 vs
␻ SO2 (wagging)
Fig. 3. DTA–TG curves of [Bi6O4(OH)4](NH2SO3)6.

9
2
A. Zahariev et al. / Thermochimica Acta 502 (2010) 90–93
◦
Fig. 5. XRD patterns of phases derived at different temperatures: (a) 320 C; (b)
◦
◦
4
(
40 C; (c) 620 C. The separate phases are denoted as follows: ( ) Bi2O2SO4;
) Bi4{NH(SO3)2}4(OH)4; ( ) [Bi6O4(OH)4](NH2SO3)6; ( ) Bi2O(SO4)2; (
)
Fig. 4. FTIR spectra of phases derived at different temperatures as follows: (a)
Bi2O(OH)2SO4.
◦ ◦ ◦ ◦
40 C; (b) 320 C; (c) 440 C; (d) 620 C.
2
of SO3 into SO4 may take place. Both changes could explain the
widening, shift and partial merging some bands within the range
mentioned.
In Fig. 5b, the formation of another known phase Bi O(SO ) is
2
4 2
◦
observed at 440 C [21].
◦
−1
(Fig. 4d) com-
At 620 C, the absorption band at 1418 cm
◦
Within the temperature range of 230–410 C (Fig. 3) in the DTA
pletely disappears. Along with the elemental analysis (Found %:
N – 0.08) of the remainder at this temperature, this reveals the
entire separation of nitrogen. In Fig. 5c, the simultaneous presence
of three oxido- and oxidohydroxidosulfates of Bi(III), i.e. Bi O SO ,
◦
curve, an endothermic peak at 300 C is obvious, and mass loss ꢁm
2
.00% (calcd. 2.30%) is registered following the TG curve. In Fig. 4b,
◦
the FTIR spectrum of the phase formed at 320 C is presented. The
figure reveals that the bands at 1553 cm and 792 cm entirely
disappear, while the new band at 1402 cm becomes more inten-
sive and shifts towards 1418 cm . This band could most likely be
explained by bending vibrations of NH-group [19]. Likewise, from
2
2
4
−1
−1
Bi O(SO ) [21] and Bi O(OH) SO [22] is clearly seen.
2 4 2 2 2 4
−1
Two consequent endothermic peaks appear in Fig. 3 at 810 and
−1
◦
840 C, respectively, coupled with substantially stronger sample’s
mass decrease (ꢁm 11.40%), which is probably caused by the evo-
lution of large amount of SO3.
◦
XRD (Fig. 5a) two new phases appear at 320 C, one of which is
the well known Bi O SO [20]. The second phase most probably
When comparing the thermal stability of [Bi O (OH) ]
2
2
4
6
4
4
corresponds to the composition containing imidosulfonate species
(NH SO )
with other similar compounds: [Bi O (OH) ]
2
3
6
6 4 4
Bi {NH(SO ) } (OH) , which is not described in the literature. One
(C11H23COO)6
[14], [Bi O (OH) ](C17H35COO)6
[15] and
4
3
2
4
4
6
4
4
can judge about the existence of this presumable composition by
the elemental analysis performed on the solid remainder after heat-
[Bi O (OH) ](NO )5·1.5H O [4] it is clearly visible that the
6
6
3
3
2
initial decomposition temperatures lie within a short range
◦
◦
ing the initial compound up to 320 C (calcd. %: N – 2.47; S – 10.16;
(180–250 C). However, while the above mentioned complexes
◦
Found %: N – 2.28; S – 10.02).
decompose completely to Bi O3 within the range 500–600 C, for
2
◦
At 410 C (Fig. 3), a new exothermic peak appears coupled with
[Bi O (OH) ](NH SO ) this temperature is significantly higher
6
4
4
2
3 6
◦
a slight mass increase which is probably due to oxygen incorpo-
(above 840 C).
ration from the air. After a short delay of the decomposition rate
Based on the results from DTA–TG, FTIR, XRD and elemental
analyses, the following most probable mechanism of the thermal
◦
(
ꢁm 2.00%; calcd. 2.30%), a large endothermic peak at 480 C cor-
◦
responding to a mass loss ꢁm 3.00% (calcd. 2.96%) is recorded.
decomposition of [Bi O (OH) ](NH SO ) within 20–620 C could
6
4
4
2
3 6

A. Zahariev et al. / Thermochimica Acta 502 (2010) 90–93
93
be proposed:
[Bi O (OH) ](NH SO )
3
6
crystallized. Furthermore, the most probable mechanism of ther-
◦
mal decomposition of [Bi O (OH) ](NH SO ) within 20–620 C is
6
4
4
2
3 6
3
6
4
4
2
described and it is in accordance with the analyses carried out.
◦
2
0–320
C
−
→
4Bi O SO + 8NH + [Bi O (OH) ](NH SO )
2
2
4
3
6
4
4
2
3
6
References
+
Bi {NH(SO ) } (OH)
4
3
2
4
4
[
[
1] G.G. Briand, N. Burford, Chem. Rev. 99 (1999) 2601–2657.
2] N. Henry, O. Mentre, F. Abraham, E.J. McLean, P. Roussel, J. Solid State Chem.
1
79 (2006) 3087–3094.
[3] B. Sundvall, Acta Chem. Scand. A 33 (1979) 219–224.
[
[
Bi O (OH) ](NH SO )
6
4
4
2
3
6
4] A.N. Christensen, M.A. Chevallier, J. Skibsted, B.B. Iversen, J. Chem. Soc. Dalton
Trans. 3 (2000) 265–270.
5] A.N. Christensen, T.R. Jensen, N.V.Y. Scarlett, I.C. Madsen, J.C. Hanson, A.
Altomare, J. Chem. Soc. Dalton Trans. 16 (2003) 3278–3282.
6] M. Girard, J. Lecomte, J. Phys. Radium 17 (1956) 9–15.
+
Bi {NH(SO ) } (OH) + 4Bi O SO + 1.5O
4
3
2
4
4
2
2
4
2
[
◦
3
20–440
C
−
→
4NH + N + 2H O + 4Bi O SO + 3Bi O(SO )
3
2
2
2
2
4
2
4
2
[
[
7] W.A. Hermann, E. Herdtweck, W. Scherer, P. Kiprof, L. Pajdla, Chem. Ber. 126
+
Bi {NH(SO ) }4(OH)
4
3
2
4
(
1993) 51–56.
[
[
8] D.S. Sagatys, E.J. O’Reilly, S. Patel, R.C. Bott, D.E. Lynch, G.S. Smith, H.L. Kennard,
Aust. J. Chem. 45 (1992) 1027–1034.
9] E. Asato, W.L. Driessen, R.A.G. De Graaff, F.B. Hulsbergen, J. Reedijk, Inorg. Chem.
4
Bi O SO + 3Bi O(SO ) + Bi {NH(SO ) } (OH)
2
2
4
2
4
2
4
3
2
4
4
30 (1991) 4210–4218.
◦
[10] E. Asato, C.M. Hol, F.B. Hulsbergen, N.T.M. Klooster, J. Reedijk, Inorg. Chim. Acta
214 (1993) 159–167.
11] A. Radecki, M. Wesolowski, Thermochim. Acta 17 (1976) 217–229.
4
40–620
C
−
→
2NH + N + SO + SO + Bi O SO + 7Bi O(SO )
3
2
2
2
2
4
2
4
2
[
+
Bi O(OH) SO
4
[12] M. Devillers, F. De Smet, O. Tirions, Thermochim. Acta 260 (1995) 165–185.
2
2
[
[
13] P. Kiprof, W. Scherer, L. Pajdla, E. Herdtweck, W.A. Herrmann, Chem. Ber. 125
1992) 43–46.
14] A.V. Minina, Y.M. Yukhin, B.B. Bokhonov, I.A. Vorsina, Y.I. Mikhailov, L.E.
Danilova, Chem. Sust. Develop. 11 (2003) 371–378.
(
4
. Conclusion
[15] Y.M. Yukhin, K.I. Mikhailov, B.B. Bokhonov, I.A. Vorsina, Chem. Sust. Develop.
2 (2004) 403–408.
1
[
[
[
16] G.A. Benson, W.J. Spillane, Chem. Rev. 80 (1980) 151–186.
17] D. Philip, A. Eapen, G. Aruldhas, J. Solid State Chem. 116 (1995) 217–223.
18] K. Inumaru, A. Ono, H. Kubo, M. Misono, J. Chem. Soc. Faraday Trans. 94 (1998)
1765–1770.
19] M. Tatsuo, J. Mol. Spectrosc. 4 (1960) 155–167.
20] JCPDS 41-0688.
During investigation of the interaction between Bi(III) and sul-
famic acid in aqueous medium, at ambient temperature and pH
.0–1.2, a compound with composition [Bi O (OH) ](NH SO ) is
prepared. This compound is characterized by various analytical
methods: elemental analysis, DTA–TG, FTIR and XRD. The results
from these analyses reveal that the substance obtained is well
1
6
4
4
2
3 6
[
[
[
21] JCPDS 78-2087.
[22] JCPDS 76-1102.