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.
Similar content being viewed by others
References
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.
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.
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.
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.
Ichikawa M, Gustafsson T, Olovsson I. K3H(SeO4)2 at 297 and 30 K. Acta Cryst. 1994;C50:330–2.
Ichikawa M, Sato S, Komukae M, Osaka T. Structure of ferroelastic K3H(SeO4)2. Acta Cryst. 1992;C48:1569–71.
Makarova IP. Superprotonics-crystals with rearranging hydrogen bonds. Phys Solid State. 2015;57:442–9.
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.
Ramasastry C, Subba Ramaiah K. Electrical conduction in Na3H(SO4)2 and (NH4)3H(SO4)2 crystals. J Mater Sci. 1981;16:2011–6.
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.
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.
Kawahara A, Yamakawa J, Yamada T, Kobashi D. Synthetic magnesium sodium hydrogen monophosphate: MgNa3H(PO4)2. Acta Cryst. 1995;C51:2220–2.
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.
Takagi S, Mathew M, Brown WE. A glaserite-type structure: calcium tripotassium hydrogenbis(phosphate), CaK3H(PO4)2. Acta Cryst. 1983;C39:166–70.
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.
Lehr JR, Brown EH, Frazier AW, Smith JP, Thrasher RD. Crystallographic properties of fertilizer compounds. Tenne Valley Auth Chem Eng Bull. 1967;6.
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.
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.
Hadži D. Infrared spectra of strongly hydrogen-bonded systems. Pure Appl Chem. 1965;11:435–53.
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.
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.
Choi BK, Lee MN. Raman spectra of the NaH2PO4 crystals. J Raman Spectrosc. 1989;20:11–5.
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.
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.
Nakamoto K. Infrared and Raman spectra of inorganic and coordination compounds, Part A. 5th ed. New York: A Wiley-Intersience; 1997. p. 199.
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.
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.
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.
Averbuch-Pouchot MT, Durif A. Topics in phosphate chemistry. Singapore: World Scientific Publishing Co. Pte., Ltd.; 1996.
Durif A. Crystal chemistry of condensed phosphates. New York: Plenum Press; 1995.
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.
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.
Nabar MA, Dalvi AP. Thermische zersetzung und röntgendiffraktometrische untersuchungen an BaHAsO4·H2O. Monatshefte für Chemie. 1978;109:673–9.
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.
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.
Baran EJ, Schwendtner K, Kolitsch U. Vibrational spectra of three new diarsenates containing scandium(III). J Raman Spectrosc. 2006;37:1335–40.
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.
Baran EJ, Weil M. Vibrational spectra of Cd2As2O7. J Raman Spectrosc. 2004;35:178–80.
Baran EJ, Weil M. Single-crystal Raman study of erythrite, Co3(AsO4)2 ·8H2O. J Raman Spectrosc. 2004;35:178–80.
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
Corresponding author
Rights and permissions
About this article
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
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-016-5782-2