Archive / Volume LXXIII 2023

Yaroslav KOVALYSHYN, Olga KURYSHKO, Mykola KOROVYAKOV

Ivan Franko National University of Lviv, Kyryla i Mefodiya Str., 6, 79005 Lviv, Ukraine
e-mail: yaroslav.kovalyshyn@lnu.edu.ua

DOI: https://doi.org/10.37827/ntsh.chem.2023.73.059

SYNTHESIS OF IRON (III) VANADATE FROM AQUEOUS SOLUTIONS

It is known from the literature that the synthesis of iron vanadate goes through the stage of formation of polyvanadates. Most of the described synthesis processes were carried out at high temperatures. However, the course of these processes was not analyzed in detail. The synthesis of iron vanadates from aqueous solutions at different ratios between the reacting components at room temperature was studied. At a molar ratio of NaVO₃ : Fe(NO₃)₃ equal to 1, the yield of FeVO₄ was 50%. Increasing the molar ratio of NaVO₃ : Fe(NO₃)₃ to 2 and 3 led to an increase in product yield. Judging by the masses of the precipitates obtained, it is possible to predict the formation of iron di- and trivanadates under these conditions. A further increase in the molar excess of sodium vanadate, on the contrary, led to a decrease in the mass of the precipitate formed.
The dependence of the optical density on the concentration of iron ions in solutions, when using sulfosalicylic acid as a reagent, was studied, and a calibration graph was constructed.
The kinetics of reactions at different ratios between reactants were investigated. The dependences of concentrations on time in different coordinates were analyzed. The obtained results indicate that at the initial moment there is a rapid formation of sediment and a sharp decrease in the concentration of iron ions. After that, the reaction slows down, the rate of change in the concentration of iron ions is described by the equation of the first order. This is confirmed by the linear dependence of the logarithm of concentration on time for reaction mixtures in the time period of 5-100 min. In the future, the reaction slows down to an even greater extent, and for long process times, close to linear dependences are observed for the change in the square of the inverse concentration of iron ions over time. Slowing of the process and higher concentrations of iron ions compared to those that would be the case if the first order is preserved at long process times can be explained by aggregation and increase in the size of vanadate particles. Accordingly, the surface area of the phase separation will decrease, which will lead to a sharper decrease in the speed of the process. Regardless of the choice of reaction order in the calculations, when the molar excess of sodium vanadate is reduced from 4 to 1, the speed of the process increases.

Keywords: iron vanadate, heterogeneous reaction, rate constant.

References:

1. Rajaji U., Kumar Y.K., Chen, S.M. et al. Deep eutectic solvent synthesis of iron vanadate-decorated sulfur-doped carbon nanofiber nanocomposite: electrochemical sensing tool for doxorubicin. Microchim. Acta. 2021. Vol.188. P. 303. (https://doi.org/10.1007/s00604-021-04950-7).
2. Munseok S.Ch., Setiawan D., Kim H.J., Hong S.-T. Layered Iron Vanadate as a High-Capacity Cathode Material for Nonaqueous Calcium-Ion Batteries. Batteries. 2021. Vol. 7(3). P. 54. (https://doi.org/10.3390/batteries7030054).
3. Routray K., Zhou W., Kiely Ch. J., Wachs I.E. Catalysis Science of Methanol Oxidation over Iron Vanadate Catalysts: Nature of the Catalytic Active Sites. ACS Catal. 2011. Vol. 1. P. 54–66.(https://doi.org/10.1021/cs1000569).
4. Chen L., Liu F., Li D. Precipitation of crystallized hydrated iron (III) vanadate from industrial vanadium leaching solution. Hydrometallurgy. 2011. Vol. 105 (3–4). P. 229–233. (https://doi.org/10.1016/j.hydromet.2010.10.002).
5. Rao N.S., Palanna O.G. Electrical and magnetic studies of iron (III) vanadate. Bull. Materials Sci. 1995. Vol. 18. P. 229–236. (https://doi.org/10.1007/BF02749660).
6. Adeniyi K.O., Osmanaj B., Manavalan G., Samikannu A., Mikkola J.-P., Avni B., Boily J.-F., Tesfalidet S. Engineering of layered iron vanadate nanostructure for electrocatalysis: Simultaneous detection of methotrexate and folinic acid in blood serum. Electrochim. Acta. 2023. Vol. 458(1). P. 142538. (https://doi.org/10.1016/j.electacta.2023.142538).
7. Mosleh M. Nanocrystalline iron vanadate: facile morphology-controlled preparation, characterization and investigation of optical and photocatalytic properties. J Mater Sci: Mater Electron. 2017. Vol. 28. P. 5866–5871. (https://doi.org/10.1007/s10854-016-6259-6).
8. Poizot Ph., Laruelle S., Touboul M., Tarascon J.-M. Wet-chemical synthesis of various iron(III) vanadates(V) by co-precipitation route. C.R. Chimie. 2003. Vol. 6. P. 125–134. (https://doi.org/10.1016/S1631-0748(03)00015-8).
9. Huang L., Shi L., Zhao X., Xu J., Li H., Zhang J., Zhang D. Hydrothermal growth and characterization of length tunable porous iron vanadate one-dimensional nanostructures. Cryst. Eng. Comm. 2014. Vol. 16. P. 5128–5133. (https://doi.org/10.1039/C3CE42608D).
10. Kesavan G., Pichumani M., Chen Sh.-M. Influence of Crystalline, Structural, and Electrochemical Properties of Iron Vanadate Nanostructures on Flutamide Detection. ACS Appl. Nano Mater. 2021. Vol. 4(6). P. 5883–5894. (https://doi.org/10.1021/acsanm.1c00802).
11. Patoux S., Richardson T.J. Lithium insertion chemistry of some iron vanadates. Electrochem. Comm. 2007. Vol. 9(3). P. 485−491. (https://doi.org/10.1016/j.elecom.2006.10.006).
12. Ozer D., Tunca E.T., Oztas N.A. Effects of fuel type on iron vanadate nanocatalyst synthesized by solution combustion method for methylene blue degradation. J. Nanopart. Res. 2021. Vol. 23 (8). P. 167. (https://doi.org/10.1007/s11051-021-05303-4).
13. КND 211.1.4.040-95 Method of photometric determination of iron (III) and iron (II, III) with sulfosalicylic acid in wastewater. (in Ukrainian).

How to Cite

Kovalyshyn Ya., Kuryshko O., Korovyakov M. SYNTHESIS OF IRON(III) VANADATE FROM AQUEOUS SOLUTIONS. Proc. Shevchenko Sci. Soc. Chem. Sci. 2023. Vol. LXX. P. 59-67.

Download the pdf