Skip to main content
Log in

Characterization and thermal decomposition of Mg2KH(AsO4)2·15H2O

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

In this work, we present first data on the infrared and Raman spectroscopic characteristics, thermal analysis and solid-state transformations of Mg2KH(AsO4)2·15H2O, which is a unique example of an acid salt containing dimeric units [H(AsO4)2] in its crystal structure. The infrared and Raman spectra recorded at ambient conditions have been studied, and an assignment of the observed vibrational bands has been proposed considering the crystal structure data. The thermal behavior of Mg2KH(AsO4)2·15H2O has been investigated by simultaneous TG/DTA/mass spectrometry experiments in the temperature range up to 1000 °C at different heating rates, and new data on the thermal stability and thermal dehydration of Mg2KH(AsO4)2·15H2O have been obtained. The phase composition after the dehydration processes in the temperature interval of 300–650 °C has been studied by combination of powder XRD and IR spectroscopic analyses. The spectroscopic and thermal properties of Mg2KH(AsO4)2·15H2O have been compared to those of the isostructural phosphate salt Mg2KH(PO4)2·15H2O.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Šoptrajanov B, Stefov V, Kuzmanovski I, Jovanovski G. Fourier transform infrared and Raman spectra of manganese hydrogenphosphate trihydrate. J Mol Struct. 1999;482–483:103–7.

    Article  Google Scholar 

  2. Koleva V, Effenberger H. Crystal chemistry of M[PO2(OH)2]2·2H2O compounds (M = Mg, Mn, Fe, Co, Ni, Zn, Cd). Structural investigation of the Ni-, Zn- and Cd-salts. J Solid State Chem. 2007;180:956–67.

    Article  CAS  Google Scholar 

  3. Koleva V, Stefov V, Najdoski M, Cahil A. Vibrational spectra of cobalt dihydrogen phosphate dihydrate, Co(H2PO4)2·2H2O. Vibr Spectrosc. 2012;62:229–37.

    Article  CAS  Google Scholar 

  4. Koleva V, Stefov V. Phosphate ion vibrations in dihydrogen phosphate salts of the type M(H2PO4)2·2H2O (M = Mg, Mn Co, Ni, Zn, Cd): spectra–structure correlations. Vibr Spectrosc. 2013;64:89–100.

    Article  CAS  Google Scholar 

  5. Ichikawa M, Gustafsson T, Olovsson I. K3H(SeO4)2 at 297 and 30 K. Acta Cryst. 1994;C50:330–2.

    CAS  Google Scholar 

  6. Ichikawa M, Sato S, Komukae M, Osaka T. Structure of ferroelastic K3H(SeO4)2. Acta Cryst. 1992;C48:1569–71.

    CAS  Google Scholar 

  7. Makarova IP. Superprotonics-crystals with rearranging hydrogen bonds. Phys Solid State. 2015;57:442–9.

    Article  CAS  Google Scholar 

  8. Ichikawa M, Gustafsson T, Motida K, Olovsson I, Gesi K. Temperature dependence of lattice constants of Rb3H(SeO4)2, a ‘zero-dimensional’ H-bonded crystal. Ferroelectrics. 1990;108:307–12.

    Article  CAS  Google Scholar 

  9. Ramasastry C, Subba Ramaiah K. Electrical conduction in Na3H(SO4)2 and (NH4)3H(SO4)2 crystals. J Mater Sci. 1981;16:2011–6.

    Article  CAS  Google Scholar 

  10. Pawlowski A, Pawlaczyk C, Hilzcer B. Electric conductivity in crystal group Me3H(SeO4)2 (Me: NH4 +, Rb+, Cs+). Solid State Ion. 1990;44:17–9.

    Article  CAS  Google Scholar 

  11. Komukae M, Osaka T, Kaneko T, Makita Y. Dielectric study of phase transitions in Cs3H(SeO4)2 and its isotope effect. J Phys Soc Jpn. 1985;54:3401–5.

    Article  CAS  Google Scholar 

  12. Kawahara A, Yamakawa J, Yamada T, Kobashi D. Synthetic magnesium sodium hydrogen monophosphate: MgNa3H(PO4)2. Acta Cryst. 1995;C51:2220–2.

    CAS  Google Scholar 

  13. Zouari N, Ben Amor M, Mhiri T, Daoud A, Reau JM. Electrical properties of magnesium sodium hydrogen monophosphate: MgNa3H(PO4)2. J Alloys Compd. 1996;240:70–5.

    Article  CAS  Google Scholar 

  14. Takagi S, Mathew M, Brown WE. A glaserite-type structure: calcium tripotassium hydrogenbis(phosphate), CaK3H(PO4)2. Acta Cryst. 1983;C39:166–70.

    CAS  Google Scholar 

  15. Chisholm CRI, Toberer ES, Louie MW, Haile SM. Engineering the next generation of solid state proton conductors: synthesis and properties of Ba3−x K x H x (PO4)2. Chem Mater. 2010;22:1186–94.

    Article  CAS  Google Scholar 

  16. Lehr JR, Brown EH, Frazier AW, Smith JP, Thrasher RD. Crystallographic properties of fertilizer compounds. Tenne Valley Auth Chem Eng Bull. 1967;6.

  17. Takagi S, Mathew M, Brown WE. Water-rich hydrates. The structures of dimagnesium potassium hydrogenbis(arsenate) 15-hydrate and dimagnesium potassium hydrogenbis (phosphate) 15-hydrate. Acta Cryst. 1982;B38:44–50.

    Article  CAS  Google Scholar 

  18. Koleva V, Stefov V, Najdoski M, Cahil A. Thermal, spectral and microscopic studies of water-rich hydrate of the type Mg2KH(PO4)2·15H2O. Thermal transformations. Thermochim Acta. 2015;619:20–5.

    Article  CAS  Google Scholar 

  19. Hadži D. Infrared spectra of strongly hydrogen-bonded systems. Pure Appl Chem. 1965;11:435–53.

    Google Scholar 

  20. Koleva V, Stefov V, Cahil A, Najdoski M, Šoptrajanov B, Engelen B, Lutz HD. Infrared and Raman studies of manganese dihydrogen phosphate dihydrate, Mn(H2PO4)2·2H2O. Part II. Region of the internal OH group vibrations”. J Mol Struct. 2009;919:164–9.

    Article  CAS  Google Scholar 

  21. Unterderweide K, Engelen B, Boldt K. Strong hydrogen bonds in acid selenites: correlation of infrared spectroscopic and structural data. J Mol Struct. 1994;322:233–9.

    Article  CAS  Google Scholar 

  22. Choi BK, Lee MN. Raman spectra of the NaH2PO4 crystals. J Raman Spectrosc. 1989;20:11–5.

    Article  CAS  Google Scholar 

  23. Stefov V, Šoptrajanov B, Spirovski F, Kuzmanovski I, Lutz HD, Engelen B. Infrared and Raman spectra of magnesium ammonium phosphate hexahydrate (struvite) and its isomorphous analogues. I. Spectra of protiated and partially deuterated magnesium potassium phosphate hexahydrate. J Mol Struct. 2004;689:1–10.

    Article  CAS  Google Scholar 

  24. Abdija Z, Najdoski M, Koleva V, Runčevski T, Dinnebier RE, Šoptrajanov B, Stefov V. Preparation, structural, thermogravimetric and spectroscopic study of magnesium potassium arsenate hexahydrate. Z Anorg Allg Chem. 2014;640:3177–83.

    Article  CAS  Google Scholar 

  25. Nakamoto K. Infrared and Raman spectra of inorganic and coordination compounds, Part A. 5th ed. New York: A Wiley-Intersience; 1997. p. 199.

    Google Scholar 

  26. Martens W, Frost RL, Theo Kloprogge J. Raman spectroscopy of synthetic erythrite, partially dehydrated erythrite and hydrothermally synthesized dehydrated erythrite. J Raman Spectrosc. 2003;34:90–5.

    Article  CAS  Google Scholar 

  27. Marchewka MK, Baran J. Comparative study of vibrational spectra of Rb4LiH3(SO4)4, K4LiH3(SO4)4, K4LiH3(SeO4)4, Na5H3(SeO4)4·2H2O and Na2SeO4·H2SeO3·H2O crystals. Polarized infrared and Raman studies. Spectrochim Acta. 2004;A60:201–10.

    Article  Google Scholar 

  28. Hadži D, Orel B, Novak A. Infrared and Raman spectra of some acid salts containing crystallographically symmetric hydrogen bonds. Spectrochim Acta. 1973;29A:1745–53.

    Google Scholar 

  29. Averbuch-Pouchot MT, Durif A. Topics in phosphate chemistry. Singapore: World Scientific Publishing Co. Pte., Ltd.; 1996.

    Book  Google Scholar 

  30. Durif A. Crystal chemistry of condensed phosphates. New York: Plenum Press; 1995.

    Book  Google Scholar 

  31. Frost RL, Palmer SJ, Rogson RE. Thermal stability of newberyite Mg(PO3OH)·3H2O. A cave mineral from Skipton Lava Tubes, Victoria, Australia. J Therm Anal Calorim. 2012;107:1143–6.

    Article  CAS  Google Scholar 

  32. Ortiz E, Piñeres I, León C. On the low- to high proton-conducting transformation of a CsHSO4–CsH2PO4 solid solution and its parents. Physical or chemical nature? J Therm Anal Calorim. 2016;. doi:10.1007/s10973-016-5474-y.

    Google Scholar 

  33. Nabar MA, Dalvi AP. Thermische zersetzung und röntgendiffraktometrische untersuchungen an BaHAsO4·H2O. Monatshefte für Chemie. 1978;109:673–9.

    Article  CAS  Google Scholar 

  34. Berardelli ML, Galli P, La Ginestra A, Massucci MA, Varshney KG. Crystalline zirconiurn (iv) hydrogenarsenate hydrogenphosphate monohydrate: synthesis, ion-exchange properties, and thermal behaviour. J Chem Soc Dalton Trans. 1985;1737–42.

  35. Losilla ER, Salvado MA, Aranda MAG, Cabeza A, Pertierra P, García-Granda S, Bruque S. Layered acid arsenates α-M(HAsO4)2 H2O(M = Ti, Sn, Pb): synthesis optimization and crystal structures. J Mol Struct. 1998;470:93–104.

    Article  CAS  Google Scholar 

  36. Baran EJ, Schwendtner K, Kolitsch U. Vibrational spectra of three new diarsenates containing scandium(III). J Raman Spectrosc. 2006;37:1335–40.

    Article  CAS  Google Scholar 

  37. Mihajlović T, Libowitzky E, Effenberger H. Synthesis, crystal structure, infrared and Raman spectra of Sr5(As2O7)2(AsO3OH). J Solid State Chem. 2004;177:3963–70.

    Article  Google Scholar 

  38. Baran EJ, Weil M. Vibrational spectra of Cd2As2O7. J Raman Spectrosc. 2004;35:178–80.

    Article  CAS  Google Scholar 

  39. Baran EJ, Weil M. Single-crystal Raman study of erythrite, Co3(AsO4)2 ·8H2O. J Raman Spectrosc. 2004;35:178–80.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors are pleased to acknowledge the financial support of the Bulgarian Academy of Sciences and Macedonian Academy of Sciences and Arts.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Violeta Koleva.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Koleva, V., Stefov, V. & Najdoski, M. Characterization and thermal decomposition of Mg2KH(AsO4)2·15H2O. J Therm Anal Calorim 127, 1911–1919 (2017). https://doi.org/10.1007/s10973-016-5782-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-016-5782-2

Keywords

Navigation