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ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2006, Vol. 51, No. 3, pp. 357361. Pleiades Publishing, Inc.

., 2006. Original Russian Text N.V. Podvalnaya, V.L. Volkov, 2006, published in Zhurnal Neorganicheskoi Khimii, 2006, Vol. 51, No. 3, pp. 404408.

SYNTHESIS AND PROPERTIES OF INORGANIC COMPOUNDS

Composition and Formation Kinetics of Sodium Polyvanadates in Vanadium(IV, V) Solutions


N. V. Podvalnaya and V. L. Volkov
Institute of Solid State Chemistry, Ural Division, Russian Academy of Sciences, ul. Pervomaiskaya 91, Yekaterinburg, 620219 Russia
Received March 7, 2005

AbstractWe study how VO2+ ions affect the composition and formation kinetics of polyvanadate precipitates in solutions with 1 3 at 8090C. The compounds have the general formula Na2.1 xH V y V 12 y O31 nH2O (0 x 1.1, 0.2 y 2.3, 0.1 1.4). The maximal vanadium(IV) concentration in the precipitates (y = 2.2 and 2.3) is achieved for the V4+/V5+ ratio in the solution equal to 0.5 and 0.3 and pH of 1.7 and 3.0, respectively. The polyvanadate precipitation at pH 1.7 has a long induction period, which is not observed when V4+/V5+ > 0.02. In the solutions with pH 3.0, the precipitation occurs only when VO2+ are added. The processes are controlled by second-order reactions on the polyvanadate surface. DOI: 10.1134/S0036023606030041
4+ 5+

Precipitation of solids from watersalt systems of vanadium(V) and vanadium(IV) receives insufcient attention in hydrochemical investigations. In particular, only vanadium(V) ions are considered in reference to the hydrolytic precipitation of alkali [2] and alkalineearth [3] polyvanadates. However, VO2+ or VO()+ cations are contained in process solutions and vanadates obtained from acid solutions always contain vanadium(IV) [4]. Mixed-valence vanadium compounds prepared in mild hydrochemical processes can serve as precursors for high-temperature compounds [5, 6]. Therefore, it is topical to investigate the composition and formation conditions of vanadium compounds in aqueous solutions. Na4H[ V y V 10 y Om] nH2O (x = 0 or 1, y = 2.8, m = 2426) compounds crystallized from a concentrated NaVO3 and VOSO4 solution under an inert atmosphere at 070C and pH 4.06.5 [7]. These compounds, when prepared in [8] at VOSO4 /NaVO3 = 0.2 0.25, cV = 0.2 mol/l, and room temperature, had the composition Nax V y V 10 y Om nH2O (x 4, y 1.5).
4+ 5+ 4+ 5+

EXPERIMENTAL The starting chemicals used are NaVO3 , VOSO4 , and H2SO4 of at least an analytical grade. The experiments are carried out at 80 or (90 0.5)C in a thermostat. Precipitates are separated by ltration, washed with ethanol, and dried in air at room temperature. The sodium is determined using atomic absorption. The vanadium is determined volumetrically. The phase composition of the compounds is derived from their IR spectra and X-ray diffraction patterns, which are recorded on a Specord 75 spectrometer and a STADI-P apparatus (Cu 1 radiation), respectively. The formation kinetics of sodium polyvanadates are studied in the batch mode. The kinetics are traced as the change in the total vanadium [vanadium(V) + vanadium(IV)] concentration in the solution. RESULTS AND DISCUSSION Vanadium(V) in acid solutions (pH 3) exists in 4 + two ions (2V10 O 28 and VO 2 [11]). These ions form, with sodium cations, polyvanadate precipitates by the reactions 10Na+ + 62 V10 O 28 + 14H+ = 5Na2V12O31 + 13H2O, (1) 2Na+ + 12 VO 2 + 7H2O = Na2V12O31 + 14H+,
4 + + 4

Polyvanadate Nax(VO)zHt[ V y V 12 y Om] nH2O (3 > x + 2z + t 2, y 2) precipitated in the pH range of 1.1 2.0 [8, 9]. The solubility data [10] imply that this com4+ 5+ pound is formulated as NaxHz x V y V 12 y Om nH2O with 1.4 x 2.0, 0 y 1.9, and 2.5n + 0.5z 10. The composition and formation kinetics of mixedvalence sodium polyvanadates at high temperatures in the NaVO3VOSO4H2OH2SO4 system have not been studied; therefore, we study them in this work.

4+

5+

(2)

2Na+ + H 2 V 10 O 28 + 2 VO 2 = Na2V12O31 + H2O. (3) Sodium polyvanadates of the general formula 4+ 5+ Na2.1 xHx V y V 12 y O31 nH2O, where 0 x 1.1, 0.2 y 2.3, and 0.1 1.4, precipitate from the

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PODVALNAYA, VOLKOV

NaVO3VOSO4H2OH2SO4 system at 8090C, 1 3, and the total vanadium concentration of 0.06 0.20 mol/l. The polyvanadates contain signicant amounts of vanadium(IV) and have the structure of
(HOH) Na2 V 12 O31 nH2O Na2 V 2 V 10 O30 nH2O
4+ 5+ 5+

sodium polyvanadate Na2 V 12 O31 nH2O. These compounds are nearly X-ray amorphous. They can be identied by their IR spectra, in which absorption peaks are observed at the frequencies (cm1) listed below.
(V4+=O) 960 (VOH) 920 (VOV) 765 765 (VO) 525 530

5+

(V5+=O) 1000 1010

1600 1600

Figure 1 displays the plots of Na+ and V4+ concentrations in the precipitates and the pH of the ltrates as functions of the V4+/V5+ ratio in 0.2 M vanadium solutions with pH 1.7, where decavanadate ions exist [11]. An addition of VO2+ cations to a vanadium(V) solution abruptly increases the vanadium(IV) concentration in the precipitates and decreases the pH of the ltrates
x, y, mol 1 2.0 2.2 1.5 pH

when in the range 0 < V4+/V5+ 0.5. When V4+/V5+ > 0.5, the aforementioned parameters remain almost unchanged. However, the Na+ content of the polyvanadates decreases continuously. When a 0.06 M vana+ dium solution with pH 1.7 (the region of VO 2 formation [11]) is doped with VO 2 cations, the pH in the ltrate rst decreases to 1.4 (Fig. 2), due to remnant decavanadate ions. When V4+/V5+ > 0.03, the pH starts to increase abruptly to reach 2.32.4 near V4+/V5+ = 0.16; then, at higher VO2+ concentrations in the starting solution, the pH decreases. The Na+ concentration in the precipitate decreases appreciably (from 2 to 1.2 mol per 12 vanadium moles) until the pH reaches 2.32.4; in the range 2.35 2.1, the Na+ concentration changes from 1.2 to 1.1 mol per 12 vanadium moles. Sodium polyvanadate at pH 3 precipitates only from mixed solutions containing vanadium(V) and vanadium(IV). The composition of the solid phase in the range 0.16 V4+/V5+ 0.83 is formulated as 4+ 5+ Na2 V y V 12 y O31 nH2O, where 1.8 y 2.2 and 0.9 1.2. The diagram of the vanadium ion state in 4 solutions [11] shows that NaHV10 O 28 complexes [12, 13] exist at pH 3. Therefore, mixed-valence polyvanadates under the specied conditions are precipitated by the reaction NaHV 10 O 28 + 2VO
4 2+ +

2 1.0 1.8

+ ( 1 x )Na
+

0.5 3

= Na 2 x H x V 12 O 30 + ( 1 x )H .
1.4 4

(4)

2 V4+/V5+, mol/mol

Fig. 1. Plots of (1) V4+ concentration, (2) Na+ concentration, and (3) pH of the ltrate vs. V4+/V5+ ratio in a 0.2 M NaVO3 + VOSO4 solution with pH 1.7 exposed at 90C for 90 min.

The solution pH should decrease in an association that matches the experimental data. For a 0.2 M solution with V4+/V5+ = 1, the pH after the polyvanadate precipitation at 90C is 2.0 (Fig. 1). The sodium concentration in the precipitate, where the Na+ cations are partially substituted by protons, likewise decreases as the sodium concentration in the solution decreases. In 0.06 M vanadium solutions, the sodium polyvanadate precipitation starts according to reaction (4), as shown by the decreasing pH (Fig. 2). As the vanadium(V) conVol. 51 No. 3 2006

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COMPOSITION AND FORMATION KINETICS OF SODIUM POLYVANADATES x, y, mol 1 2.0 2 2.2 5 pH cV, g/l 6

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1.5

4 3

1.0

1.8

2 0.5 1 1.4 0 3 2 1 30 60 90 120 150 , min 4

0.1

0.2 V4+/V5+, mol/mol

0.3

Fig. 2. Plots of (1) V4+ concentration and (3) Na+ concentration in the precipitates and (2) pH of the ltrate vs. V4+/V5+ ratio in a 0.06 M NaVO3 + VOSO4 solution with pH 1.7 exposed at 80C for 90 min.

Fig. 3. Plot of the vanadium concentration in a solution (initially 0.06 M) vs. polyvanadate precipitation time at pH 3.0, 80C, and V4+/V5+ = (1) 0.33, (2) 0.50, (3) 0.66, and (4) 0.83.

centration in the solution lowers, the stable solute spe+ cies become VO 2 cations [11, 12], which are formed by the reaction NaHV10 O 28 + 15H+ = 10 VO 2 + Na+ + 82.
4 +

(5)

nucleated. The rate curves obey the equation n = In [14] for second-order reactions proceeding on a solid surface. The rate constant of the reaction changes as a function of the VO2+ concentration in the solution in the order 0.08, 0.10, 0.06, and 0.04 for the V4+/V5+ ratios equal to 0.33, 0.50, 0.66, and 0.83, respectively. Vanadium(IV) ions have an essential kinetic effect on sodium polyvanadate precipitation by reaction (6) (Fig. 4). When the solution contains only vanadium(V), the induction (nucleation) period is long (~45 min). The induction period shortens to 20 min and disappears completely, when V4+/V5+ in the solution is 0.02 and 0.08, respectively. The rate curves are also best tted to the equation for second-order reactions (Fig. 5). The rate constant of the reaction as a function of the VO2+ concentration in the solution is 0.37, 0.39, and 0.32 for V4+/V5+ equal to 0.02, 0.08, and 0.33, respectively. As a result of the investigations, we nd that a polyvan4 5+ adate of variable composition Na2.1 xHx V y V 12 y O31 nH2O (0 x 1.1, 0.2 y 2.3, 0.1 1.4) precipitates at 8090C from acid solutions (pH 13) of vanaNo. 3 2006

This process is accompanied by a dramatic increase in solution pH (Fig. 2). After this, the pH of the ltrate decreases as a result of the hydrolysis reaction 10VO 2 + ( 2 x )Na + 2VO
+ + 2+

+ 8H 2 O
+

= Na 2 x H x V 12 O 30 + ( 16 x )H .

(6)

This sodium polyvanadate precipitation is the major process for the 0.2 M vanadium solution at 90C and pH 1.7 (Fig. 1). The results of the kinetic investigations of sodium polyvanadate formation by reaction (4) are displayed in Fig. 3. The plot of the vanadium concentration in the solution as a function of time shows a short (no longer than 10 min) induction period during which the solid is
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PODVALNAYA, VOLKOV In 40

4 2 30 3 1

20 2 3 4

10 1 4 3 0 2 1 0 30 60 90 , min 40 80 120 , min

Fig. 4. Plot of the vanadium concentration in a solution (initially 0.06 M) vs. polyvanadate precipitation time at pH 1.7, 80C, and V4+/V5+ = (1) 0, (2) 0.02, (3) 0.08, and (4) 0.33.

Fig. 5. Plot of In vs. time for polyvanadate precipitation at pH 1.7, 80C, and V4+/V5+ = (1) 0, (2) 0.02, (3) 0.08, and (4) 0.33.

dium(V) that contain sodium and VO2+ cations. When V4+/V5+ = 0.2, Na2V12O30 nH2O stoichiometry is obtained from the solution with pH 3; this phase may be regarded as the hydrated -Na2V12O30 phase (an oxide bronze [15]). The vanadium(IV)-containing sodium polyvanadate hydrates are not a product of the ion exchange of vanadium(V) in NaxHz xV12O31 nH2O for vanadium(IV) [10]. This scenario of formation of reduced polyvanadate will not enhance its precipitation. VO2+ ions enhance the formation of xV12O31 nH2O polyvanadates; the latter have a layered structure built of V2O5 polymer chains with hydrated n+ cations residing in between [4]. Therefore, the crystallization of partially reduced polyvanadates is a result of the chemical reaction between vanadium(V) and vanadium(IV) ions: the latter enhance the polymerization of VO groups and the formation of the layered structure of polyvanadates. An important result of this work is that we discovered the feasibility to precipitate vanadium from solutions through acid-free hydrolysis [17]. The precipitation is due to the reaction of VO2+ cations with decavanadate anions at pH 3 and 8090C. The residual

overall vanadium (vanadium(IV) + vanadium(V)) concentration in the solution in this process is not higher than 0.10.15 g/l. ACKNOWLEDGMENTS This work was supported by the Program for Leading Scientic Schools of the Russian Federation (project NSh-1046.2003.3). REFERENCES
1. V. G. Mizin, E. M. Rabinovich, T. P. Sirina, et al., Complex Processing of Vanadium Materials (Ural. Otd. Ross. Akad. Nauk, Yekaterinburg, 2005) [in Russian]. 2. A. A. Ivakin and V. L. Volkov, in Investigation in the Field of Mineral Salts and Oxides (Nauka, Moscow, 1965), p. 166 [in Russian]. 3. A. A. Ivakin, I. G. Chufarova, V. G. Dobysh, and L. G. Borisyuk, Zh. Neorg. Khim. 30 (4), 908 (1985). 4. V. L. Volkov, G. S. Zakharova, and V. M. Bondarenka, Xerogels of Simple and Complex Vanadates (Ural. Otd. Ross. Akad. Nauk, Yekaterinburg, 2001) [in Russian]. 5. G. Liu and J. E. Greedan, J. Solid State Chem. 114 (2), 499 (1995).
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COMPOSITION AND FORMATION KINETICS OF SODIUM POLYVANADATES 6. V. L. Volkov, N. V. Podvalnaya, and M. Yu. Yanchenko, RF Patent No. 2225656, Byull. Izobret., No. 7 (2004). 7. S. Ostrowetsky, Bull. Soc. Chim. Fr., No. 3, 1012 (1964). 8. A. A. Ivakin, M. V. Kruchinina, O. V. Koryakova, and M. P. Glazyrin, Zh. Neorg. Khim. 33 (9), 2423 (1988). 9. A. A. Ivakin, M. V. Kruchinina, and O. V. Koryakova, Zh. Neorg. Khim. 32 (12), 3075 (1987). 10. A. A. Ivakin, M. V. Kruchinina, and O. V. Koryakova, Zh. Neorg. Khim. 34 (9), 2203 (1989). 11. T. I. C. Rossotti and H. Rossotti, Acta Chem. Scand. 10 (6), 957 (1956).

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12. A. A. Ivakin and A. A. Fotiev, The Chemistry of Pentavalent Vanadium in Aqueous Solutions (UNTs AN SSSR, Sverdlovsk, 1971) [in Russian]. 13. G. Schwarzenbach and G. Geier, Helv. Chim. Acta 46, 906 (1963). 14. A. E. Nielsen, Acta Chem. Scand. 13 (4), 784 (1959). 15. V. L. Volkov, Interstitial Phases Based on Vanadium Oxides (UNTs AN SSSR, Sverdlovsk, 1987) [in Russian]. 16. V. L. Volkov and N. V. Podvalnaya, Zh. Neorg. Khim. 45 (12), 2064 (2000) [Russ. J. Inorg. Chem. 45 (12), 1912 (2000)]. 17. N. V. Podvalnaya and V. L. Volkov, RF Patent No. 2187570, Byull. Izobret., No. 23 (2002).

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