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    Acta Chemica Scandinavica 1997 51 387

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    ese Che Sada, 197 387-391 pel 9 dee Chin Sona 197 Tre ahs ned an ccrteaica SEANDINAVICA Crystal Structure of the Double Carbonate K,Caz(CO3)3 Camilla Winbo,* Dan Bostrém** and Matthias Gébbels” “Department of Inorganic Chemistry, Umea University, $-901 87 Umed, Sweden and "Institut far Kristallographie, RWTH Aachen, D-52056 Aachen, Germany Winbo, C., BostrOm, D. and Gabbels, M., 1997. Crystal Structure ofthe Double Carbonate K;Cas{CO,), ~ Acta Chem, Seand. 51: 387-391. © Acta Chemica Scandinavica 1997, ‘The crystal structure of K,Ca,(CO,), was determined from single-crystal X-ray difracton data. This double carbonate erytalises in the spsce BrouP B3 (No 146). with unitoed dimensions «= 15010(4), = 8615) Ay 12639(9) AY and 2 ~6. Anisotropic refinements gave Ry ~ 0.018 for 816 snigue refections. The two eystallogaphicaly ferent carbonate ions are located in Colgrans around the thce-fold sacs at which 1 of the cations ae stated (one ‘Ca** and one K"), the remainder being located in general positions between the carbonate coluris,‘The carbouats ona are more or lew ocned eat th (001 plane and donot form an unequivocal layered stactre Experimental and ealcoted powder Xray cifraction date for KyCay(CO,), are presented ‘The first published investigation of the K,CO,-CaCO, system was performed by Nigali? in 1916, Niggli studied the KCOy-rich side of the system, in I atm of CO, and in the temperature range 700-900°C, and found one intermediate phase; K:Ca(COs):, melting at 813°C. Kroger et al? investigated the phase relations and pre- sented a phase diagram for the binary system KCO,- CaCO, in the temperature range 500-1400°C, at approximately 50>bar. They found two intermediate phases, the double carbonates K,Ca(CO,); and K,Cax(CO,),. Walenta® describes the occurrence of a new carbonate mineral containing calcium and potassium as main cation components. From optical crystallog- raphy, Walenta concluded that this new mineral belongs to the ‘rhombohedral system’. Cooper et al.‘ determined the phase relations in the ternary system NaCO,- K,CO,-CaCOy at kbar. In the binary sub-system K3CO,-CaC0O, they describe three intermediate phases, two K,Ca(CO,), phases, fairchildite and btscli (hich is low temperature modification of the former) and an unnamed phase, K,Ca,(CO,),, referred to a8 phase A. K,Ca,(CO,), is an incongruently melting phase (810°C) which decomposes at 512°C to calcite and batschite. The erystals of phase A are described as pale yellow-green granules, with grains that always exhibit polysynthetic twin lamellae parallel and perpendicular to the c-axis. Although this double carbonate KCa,(COs), has been known since 1943, the crystal structure has not been determined; in fact not even an unambiguous powder diffraction pattern is available, The two other "To whom correspondence should be addressed. (© Acta Chemie Scandinavia 611997) 967-201 double carbonates in the system KCO,-CaCO, have bbeen found in wood ash in partly burned fir, hemlock and other trees in the western United States.*° Fairchildite has also been identified in ash from the combustion of biomass fuels.” The aim of the present work is to determine the structure of the double carbonate K,Ca,(CO,)s by single-crystal X-ray diffraction, and to present an accur~ ate powder X-ray diffraction pattern that can serve as a reliable identification tool for this phase. Experimental ‘Synthesis. The growth of single erystals of K3Ca3(COs)s of sufficient size for single-crystal X-ray diffraction investigations cannot easily be carried out under normal pressure conditions. On the one hand, the material decomposes at higher temperatures before melting, and on the other, solution growth may fail due to the poor solubility of the compounds. A high-pressure technique using a sealed container seemed to present a more promising approach. As long as the piston-cylinder tech- nique was available for the single-crystal growth experi- ‘ment, a minimum pressure of 10 kbar had to be chosen ‘The melting point of 810°C at 1 kbar for KCa3(CO,)s shifts to a higher temperature at 10 kbar if the compound remains a stable phase, Therefore a temperature of 950°C at 10kbar was assumed to be still in the sub-solidus region. A stoichiometric mixture of dried K3CO, (Baker) and CaCO, (Riedel-deHatn) was prepared as a starting material for K;Ca,(COs)s. This mixture was heated in @ CO, atmosphere at 750°C for 11d. The new phase was assumed to be pure since, according to an X-ray 387 WINBO ET AL Fig. 1. A stereoscopic view of the structure per (special postion a) and Ca(2) and Ki2) in gener powder diffractogram, no traces of the starting compon- ents or fairchildite and batschliite could be seen, ‘This material was then placed in a sealed gold capsule that was heated at 950°C for 2h. The cooling was made by slowly decreasing the temperature by 10°C! to 750°C. After reaching 750°C the experiment was quenched simply by switching off the heater and releasing, the pressure, The resulting crystals were checked with powder X-ray diffraction, and were found to be identical to the starting material P-T calibrations of the piston-cylinder equipment were ‘made by DTA determinations of pressure temperature effects on the melting point of LiCl. At any given pressure the probable temperature uncertainty may be at most 48°C; at any temperature set point the pressure uncer- tainty (always running the experiment in the piston-out ‘mode) may be considered to be +0.5 kbar. X-Ray measurements. The material from the high-pres- sure experiments could be described as pale yellow-green granules, usually consisting of several intergrown crys- tals. Preliminary investigations were performed on a number of erystals, in the search for a suitable single crystal. The impressions of intergrown crystals from ‘optical examination and of the twin lamellae reported by Cooper er al were confirmed in Weissenberg and precession photographs. A small fragment finaly turned ut to be a single erystal suitable for an X-ray diffraction investigation. X-Ray intensity data were collected with a SYNTEX 3 automated four-cirele diffractometer using graphite- monochromated MoK% radiation at 293K. The back- ground was measured on each side of every reflection for a time equal to the peak measurement. Cell para- meters were determined by 25. reflections with 597-<20<21.92°. A psi-scan was carried out at 10 reflections selected from intensity measurement in the range 5.94 < 26 < 52.20°, Experimental details are listed in Table | Calculations were cartied out using the Xtal3.2 pro- ram package” OF a total of 8581 reflections measured, 816 unique reflections were used in the calculations. The structure was solved using direct methods. Scattering factors used (Ca?*, K*, O>, C®) were taken from Ref, 10. A Lorenz polarisation correction and an empir- ical absorption correction based on the psiscan were 388 ;ndicula to the (001)-plane. Ca(1) and Kit) a positions between the axes. oxen exu) cain oi Yai located on the three-fold axes Table 1. Crystal and experimental data for KzCaz(COs) Formula KeCag(COs)s M, 338.38 Crystal system Trigonal Space group 3 No. 148) ah 13.0104) 86153) 1262:919) 6 267 Moka 0.71073 1025.62 Pale yellow-green Crystal description Crystal sizeimm 0.12 x 0.15 «0.08 Diffractometer: Nicolet R3 upgraded by Siemens Termporature/K 293 No, of refine for col determination (20 range”) 25 (6.97 <20<21.92) ‘Sean mode 0-20 20 ranger” 5.96 <20< 602 hk range ~W

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