ISSN 0016 7029, Geochemistry International, 2011, Vol. 49, No. 7, pp. 731737. Pleiades Publishing, Ltd., 2011.

. Original Russian Text L.V. Olysych, M.F. Vigasina, L.V. Melchakova, L.P. Ogorodova, I.V. Pekov, N.V. Chukanov, 2011, published in Geokhimiya, 2011, Vol. 49, No. 7, pp. 772778.

SHORT COMMUNICATIONS

Thermal Evolution and Thermochemistry of the Cancrinite Group CarbonateOxalate Mineral

L. V. Olysycha, M. F. Vigasinaa, L. V. Melchakovaa, L. P. Ogorodovaa, I. V. Pekova, and N. V. Chukanovb
Geological Faculty, Moscow State University, Vorobevy Gory, Moscow, 119899 Russia e mail: logor@geol.msu.ru bInstitute of Problems of Chemical Physics, Chernogolovka, Moscow Oblast, 142432 Russia
Received June 2, 2009
a

Keywords: thermal analysis, calorimetry, IR spectroscopy, oxalatecancrinite, enthalpy of formation. DOI: 10.1134/S0016702911050089

INTRODUCTION This paper continues the thermal and thermo chemical studies of cancrinite group minerals that were begun by the investigation of cancrinite and can crisilite from the KhibinyLovozero alkaline complex at the Kola Peninsula, Russia [1]. The crystalline structure of cancrinite (P63 space group) is built up of 3D framework consisting of quasilayers of 6 member rings of corner connected SiO4 and AlO4 tetrahedra. The structure is penetrated by zeolite channels of two types: the broader channels arranged around six fold axis and narrower channels represented by a chain of cancrinite voids (hexagonally distorted cuboctahedra) along the three fold axis. Cancrinite cavities accom modate cations Na+ and H2O molecules, while wider channels contain Na+ and Ca2+ cations and C O 3 anions [2]. According to our data, most of cancrinite samples correspond to simplified formula: Na6Ca[Al6Si6O24](CO3) 2H2O (Z = 1). New mineral, kyanoxalite, Na7[Si67Al65O24](24)0.51 5H2O, the high water analog of cancrinite of the same space group P63, was recently found in the Lovozero Massif [3].Our IR data imply the existence of a series of can crinitekyanoxalite solid solutions, with a gradual change of proportions of carbon bearing framework off anions CO3/24. The oxalate bearing members of the cancrinite group are typomorphic postmagmatic minerals of the Lovozero Massif. In particular, kyanoxalite initially found on the Karnasurt and Alluaiv mounts [3] was recently discovered by us also on Mt. Flora. This min eral was observed in the albitized pegmatites of its northern slope, which are localized among the rocks of the layered urtitefoyaitelujavrites. The main minerals of these pegmatites are potassic feldspar, albite, nepheline, sodalite, aegirine, amphiboles of the arfvedsonitemagnesioarfvedsonite series, eudialyte,
2

and lorenzenite. In addition to proper kyanoxalite, whose IR spectrum contains intense bands of stretch 2 ing and deformation vibrations of oxalate ion 2 O 4 , and lacks bands corresponding to C O 3 vibrations (for details of IR bands of these minerals see [3]), rocks from Mt. Flora also contain intermediate phases between this mineral and cancrinite. The members of 2 2 this series with variable C O 3 /2 O 4 ratios are visu ally indistinguishable and rarely occur in one sample. Here, they substitute S bearing sodalite with forma tion of rims up to 5 mm thick, and sometimes com plete pseudomorphs up to 1 cm thick. Columnar aggregates of these minerals are formed by elongated hexagonalprismatic cornflower blue crystals. In this work, sample from Mt. Flora was studied with DTA and IR techniques to determine the thermal evolution of the intermediate member of the cancrin itekyanoxalite series as well as with high tempera ture Calvet microcalorimetry to obtain the enthalpy of its formation. EXPERIMENTAL Chemical composition of sample. Data obtained by complex methods showed that the mineral from Mt. Flora studied in this work has the following aver age composition (wt %): Na2O 20.8, K2O 0.6, CaO 0.6, Al2O3 26.5, SiO2 38.6, SO3 0.6, CO2 5.4, H2O 6.7, and sum of 99.8. Concentrations of elements with atomic numbers higher than 8 were determined using X ray analysis on a CamScan scanning electron microscope equipped with EDS Link INCA Energy (accelerating voltage of 15.7 kV, a beam current of 0.5 nA, and scan ning area of 16 16 m). The content of water was determined using Alimarin method: sample was heated to 1000C and released water was collected in an absorption tube filled with Mg(ClO4)2. The amount
2

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OLYSYCH et al.

B C D

DTA 100 300 500 700 900 1100 1300C

Fig. 1. Thermal curves of carbonateoxalate cancrinite from Mt. Flora, the Lovozero Massif: (A) 300, (B) 450, (C) 700, (D) 900.

of CO2 was measured by selective sorption: samples were heated to 1000C in oxygen flow and the released CO2 was entrapped in an absorption pipe filled with askarite. With allowance for variable C O 3 /2 O 4 ratios in the mineral, formula was calculated assuming that whole sample in general is characterized by the com parable contents of carbonate and oxalate ions, i.e., corresponds to the average member of the cancrinite kyanoxalite series. This assumption is confirmed by ratios of intensities of the corresponding IR bands (see below), as well as by amount of H2O (3.6 molecules per formula), which falls practically in the middle part between ideal values for cancrinite (2.0) and kyanox alite (5.0). The empirical formula of the studied min eral calculated for (Si + Al) = 12 is as follows: Na6.9K0.1Ca0.1Al5.4Si6.6O24(C2O4)0.4(CO3)0.4(SO4)0.1 3.6 H2O (m.m. = 1015.28 g/mole). Thermogravimetric studies of ground sample of 80 mg weight mineral were carried out using a Q 1500D (Hungary) derivatograph from room tem perature to1300, with a heating rate of 15C/min. The results of the thermal analysis (Fig. 1) showed that volatile loss starts already at 100. Two subsequent uninterrupted stages of weight loss can be identified on the TG curve: the loss of 10.2% within a range of 100
2 2

875 and 2.2% within a range of 8751300 (in total, 12.4%). IR spectroscopy. IR absorption spectra of starting mineral and its heating products (Fig. 2) were obtained using a FSM 1201 (LOMO, Russia) Fourier Spectrometer within the range of 4004000 cm1, with frequencies determined accurate to 2 cm1. Powdered samples (in the proportion 2 mg of sample per 250 mg of KBr) were pressed into transparent pel lets. The spectra were recorded at room temperature in air, with pellets of pure KBr used for comparison. The IR absorption spectrum of the carbonate oxalate cancrinite from Mt. Flora (Fig. 2a) within a range of 4001300 cm1 is close to those of cancrinite [1] and high Si kyanoxalite [3] (cm1, shshoulder): 428, 457, 569, 623, 684, 758sh (deformation vibra tions of AlSiO framework); 818 (deformation vibrations of oxalate anion): 997, 1035sh, 1119 (stretching vibrations of framework). The band of the deformation vibrations of carbonate anion with a fre quency about 860 cm1 typical of cancrinite spectrum is absent presumably due to its overlapping by intense band with maximum at 997 cm1. The range of 1300 1800 cm1 is the most important for identification of the carbon bearing members of cancrinite group. The spectrum of the described sample in this region con tains bands typical of carbonate and oxalate groups, as well as water molecules: 1371 (symmetrical stretching
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THERMAL EVOLUTION AND THERMOCHEMISTRY OF THE CANCRINITE GROUP (a) Transmittance, rel.u. Transmittance, rel.u.
818 758 759

733

(b)

3436 3536 3600

*1371 +1395 +1472 +1501 >1640 *1711

997 1035 1119

574 626 684

400 800 1200 1600 3200 3600 4000 Wave number, cm1 (c) Transmittance, rel.u.

400 800 1200 1600 3200 3600 4000 Wave number, cm1 (d) Transmittance, rel.u.
758

758

3450

990 1035 1116

428 457

434 460

*1359 +1388 +1436 +1501 >1640 *1691

569 623 684

*1350 +1389 +1441 +1550 >1638 *1685

995 1036 1116

431 459

573 626 684

431 459

400 800 1200 1600 3200 3600 4000 Wave number, cm1 (e) Transmittance, rel.u.

400 800 1200 1600 3200 3600 4000 Wave number, cm1 (f) Transmittance, rel.u.

577

687

626

1389 1447 1505

516

579

697

995

432 462

984

1096

400 800 1200 1600 3200 3600 4000 Wave number, cm1

400 800 1200 1600 3200 3600 4000 Wave number, cm1

Fig. 2. IR spectra of carbonateoxalate cancrinite from Mt. Flora, the Lovozero Massif (a) and products of its heating (bf) to temperatures: (b) 300, (c) 450, (d) 700, (e) 900, (f) 1300 (* stretching vibrations of oxalate ion, + stretching defor mation vibrations of carbonate ion, ^ deformation vibrations of water molecules).

vibrations of oxalate ion): 1395sh, 1472, 1501 (stretch ing vibrations of carbonate ions allocated in different crystallographic sites); 1640 (deformation vibrations of water molecule); 1711 (antisymmetrical stretching vibrations of oxalate ion). The region of OH stretch ing vibrations contains a wide band with three distinct components: 3436, 3536, and 3600 cm1. The profile of this band in the IR spectrum of the mineral from Mt. Flora is similar to that of high Si kyanoxalite [3]. As compared to starting sample, IR spectrum of the mineral heated to 300 (Fig. 2b) revealed stretching vibrations corresponding to the carbon bearing anions (13001800 cm1). The absorption bands correspond
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ing to the vibrations of oxalate ion became less intense and were shifted to the lower frequencies (1359 and 1691 cm1) as compared to those of the starting min eral (1371 and 1711 cm1), approaching values found in the IR spectrum of kyanoxalite [3]. This was accom panied by the change of frequencies and growth of intensity of absorption bands with maximums at 1388 and 1436 cm1 corresponding to the stretching vibra tions of carbonate ion. The band at 1501 cm1 remained practically unchanged. The region of stretching (3400 3700 cm1) and deformation (1635 cm1) vibrations of 2 shows a decrease in band intensity.
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988

1084

1110

+1390 +1441 +1500 >1638

575 626 684

3490

3531 3585

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Heating of the sample to 450 leads to the further decrease of water content (Fig. 2c), which is con firmed by the decrease in absorption in the regions of stretching and deformation vibrations of H2O mole cules. The region of stretching vibrations of carbon bearing anions demonstrates the further reorganiza tion of spectrum: a decrease in the intensity of oxalate ion bands and an increase in the intensity of O 3 , bands, especially component at 1441 cm1. IR spectrum of mineral heated to 700 (Fig. 2d) lacks bands corresponding to the stretching vibrations of oxalate ion. Simultaneous loss of water and CO2 is confirmed by the decrease of band intensities in the corresponding regions of the spectrum. In the spectrum of the sample heated to 900 (Fig. 2e), the absorption bands of 2 are already absent. The presence of carbonate ion is identified by the presence of weakened absorption bands in a range of 13801510 cm1.The spectrum range of 4001300 cm1 shows the signs of destruction of cancrinite structure. After heating to the 1300, spectrum of sample (Fig. 2f) corresponds to the nepheline type phase with residual elements of cancrinite structure [4]. Thermochemical studies were carried out on a high temperature (1000) heat flux TianCalvet micro calorimeter (Setaram, France) [5]. The enthalpy of formation was determined by high temperature melt solution calorimetry. For these purposes, pelletes made up of a pressed powdered sample weighing 2 4 (2 103) mg were dropped from room temperature into 2PbO B2O3 melt solvent placed in calorimeter at = 973 K. During calorimetric experiment on disso lution, the mineral was heated from room temperature to dissolution temperature of ( = 973K) and its dis solution in oxide melt occurred in air and was accom panied by oxidation of oxalate ion according to reac tion: C2 O 4 + 0.5O2 C O 3 + CO2. Melt used for calorimetric dissolution was obtained by fusion of lead and boron oxide in air and contains dissolved oxygen. This is confirmed in experiments on dissolution of Fe2+ bearing compounds, Fe2SiO4, FeSiO3 [6]. Thus, the enthalpy H measured in the course of experiment on mineral dissolution, in addition to the heat content of the mineral [H(973 ) H(298.15 )] and enthalpy of its dissolution dissH(973 ), also includes exothermic effect of the oxidation of oxalate anion oxidH(973 ). Eight measurements of heat effects accompanying mineral dissolution were car ried out. Value of H was determined to be 1186.4 17.1 kJ/mol (average value with error calculated with
2 2 2

probability of 95%). The value of standard enthalpy of mineral formation from elements using reactions 2.65Na 2 O + 0.05K 2 O + 2.7Al 2 O 3 + 6.6SiO 2 + 0.1CaSO 4 + 0.4Na 2 CO 3 + 3.6H 2 O + 0.4Na 2 C 2 O 4 = ( Na 6.9 K 0.1 Ca 0.1 ) ( Si 6.6 Al 5.4 O 24 ) ( CO 3 ) 0.4 ( C 2 O 4 ) 0.4 ( SO 4 ) 0.1 3.6H 2 O , can be calculated using standard thermochemical cycle supplemented by reactions related to the oxida tion of proper mineral and sodium oxalate. As was demonstrated by our experiments, the error in H = [H(973 ) H(298.15 ) + dissH(973 ) + oxidH(973 )] determined for oxalate ion by drop technique is an order of magnitude higher than values of 23% typical of such studies, which presumably indicates its incomplete oxidation during dissolution. In this relation, the total function H = [H(973 ) H(298.15 ) + oxidH(973 )] of sodium oxalate was measured by dropping 37 (2 103) mg sample from room temperature into a calorimeter at = 973 K with no solvent present. The average value of eight measurements is 88.5 1.6 kJ/mol (error was calculated with a probability of 95%). The device was calibrated by the same drop technique, by dropping reference samples, platinum and corundum Al2O3, whose thermochemical data were taken from [7]. RESULTS AND CONCLUSIONS All thermogravimetric and IR spectroscopic data show that the thermal transformation of oxalate bear ing mineral of the cancrinite series in air could be rep resented as a combination of three main volatile assisted processes: (1) loss of molecular weight at 100 875C; (2) oxidation of oxalate ion into carbonate ion: approximate temperature interval from 200250 to 2 500600; (3) decomposition of C O 3 with release of gaseous CO2 usually occurs at temperature higher than 500 and is completed at t < 1300. The release of H2O and CO2 during heating of the carbon bearing minerals of cancrinite group is well studied [1]. Most interesting fact is the oxidation of oxalate ion into carbonate ion discovered by us at least at the first stage, without removal of these anions from crystal. This reaction proceeds under air oxygen and involves breaking CC bond in the oxalate group with 2 formation of two carbonate groups: C2 O 4 + O2 = 2C O 3 . A notable shift to the lower frequencies of bands of CO stretching vibrations in the group 2 C2 O 4 , within a temperature range between 20 and 300 shows that the oxalate component in the can crinite type structure at heating experiences some
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Table 1. Thermochemical data used in calculations of the enthalpy of formation of cancrinite group minerals (kJ/mol) Component Na2O(c.) K2O(c.) Al2O3(corundum) SiO2(quartz) Na2CO3(c.) CaSO4(anhydrite) H2O(l) [Ho(973 K) Ho(298.15 K) + diss.Ho(973 K)] 111.8 0.8b 193.7 1.1b 107.38 0.59c 39.43 0.21d 241.2 0.8b 131.3 1.6c 40.9 2.5e
a f H el (298.15 K)

414.8 0.3 363.2 2.1 1675.7 1.3 910.7 1.0 1129.2 0.3 1434.5 1.5 285.8 0.1

Note: a reference data [7], baccording to data [8], c, d, e, calculated using reference data on [Ho(973 K) Ho(298.15 K)] [7] and experi mental data on diss.Ho(973 K): c [9], d [5], e [10], f calculated in [11].

transformations (which are not reversible during rapid cooling: IR spectrum was recorded from cooled sam 2 ple). It is probable that C2 O 4 groups are shifted along axis in a channel, occupying energetically more favor able position (probability of the occurrence of oxalate ions in the kyanoxalite in different structural positions is shown in [3]), or even change their configuration. The same temperature range marks the onset of oxalatecarbonate oxidation, which was recorded in IR spectrum by the decrease in the intensity of bands corresponding to the CO vibrations of the oxalate ion and increase in those of carbonate ion. During this process, only one band with frequency 1441 cm1 among all bands corresponding to the vibrations of 2 C O 3 group shows increase in intensity, which indi cates that newly formed carbonate ions preferentially migrated along zeolite channel to accommodate only one structural site. The oxidation of oxalate into car bonate was completed yet before 700. The enthalpy of formation of the studied mineral from elements was calculated using calorimetric data obtained in this work and required thermochemcial values for constituents using the following reactions:
( Na 6.9 K 0.1 Ca 0.1 ) ( Si 6.6 Al 5.4 O 24 ) ( CO 3 ) 0.4 ( C 2 O 4 ) 0.4 ( SO 4 ) 0.1

6.6SiO 2 ( c ., 298.15 ) + melt ( 973 K ) 6.6SiO 2 ( sol., 973 ) , 0.1CaSO 4 ( c ., 298.15 ) + melt ( 973 K ) ( 0.1CaO + 0.1SO 3 ) ( sol., 973 ) , 0.4Na 2 CO 3 ( c ., 298.15 ) + melt ( 973 K ) ( 0.4Na 2 O + 0.4CO 2 ) ( sol., 973 ) , 3.6H 2 O ( l ., 298.15 ) + melt ( 973 K ) 3.6H 2 O ( sol., 973 ) , 0.4Na 2 C 2 O 4 ( g ., 298.15 K ) + 0.2O 2 ( g ., 973 ) + melt ( 973 K ) ( 0.4Na 2 O + 0.8CO 2 ) ( sol., 973 ) . Thus,

(6)

(7)

(8)

(9)

(10)

reaction(1) H = reaction(310) H reaction(2) H (11) reaction(10) H = reaction(1315) H 0.4Na 2 C 2 O 4 ( c., 298.15 ) + 0.2O 2 ( g., 973 ) 0.4Na 2 CO 3 ( c., 973 ) + 0.4CO 2 ( g., 973 ) , 0.4Na 2 CO 3 ( c., 973 ) + melt ( 973 K ) ( 0.4Na 2 O + 0.4CO 2 ) ( sol., 973 ) , 0.4CO 2 ( g., 973 ) + melt ( 973 K ) ( 0.4CO 2 ) ( sol., 973 ) . (12) (13)

3.6H 2 O ( c ., 298 ) + 0.2O 2 ( g ., 973 )

+ melt ( 973 K ) ( 3.45Na 2 O + 0.05K 2 O + 2.7Al 2 O 3 + 6.6SiO 2 + 0.1CaO + SO 3 + 1.2CO 2 + + 3.6H 2 O ) ( sol. , 973 ) ,

(2)

(14)

(15)

2.65Na 2 O ( c ., 298.15 ) + melt ( 973 K ) 2.65Na 2 O ( sol., 973 ) , 0.43K 2 O ( c, 298.15 ) + melt ( 973 K ) 0.43K 2 O ( sol., 973 ) , 2.7Al 2 O 3 ( c ., 298.15 ) + melt ( 973 K ) 2.7Al 2 O 3 ( sol., 973 ) ,
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The values of enthalpies for reactions (2) and (13) were obtained in this work, while those for reactions (38) and (14) were determined earlier in experiments (Table 1), and enthalpy for reaction (9) was calculated in [11] (Table 1). The value of reaction(15)H of 1.3 0.9 kJ was estimated by us using enthalpies of dissolu tion of CaO [5], calcite [12], and reference data on heat contents and enthalpies of formation of CaO, CO2, and calcite [7]. With allowance for conditions of
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Table 2. Thermodynamic data obtained for the intermediate member of cancrinitekyanoxalite and purely oxalate kyan oxalite at T = 298.15 K Mineral Carbonateoxalate cancrinite Na6.9K0.1Ca0.1)(Si6.6Al5.4O24)(CO3)0.4 (C2O4)0.4(SO4)0.1 3.6H2O Kyanoaxalite Na7Si6Al6O24(C2O4)0.5 5H2O
Notes: * experimental data, ** calculated data.

f H el , kJ/mol 14473 21* 14555**

So, J/K mol 1023** 1093**

f G el , kJ/mol 13545** 13489**

almost infinite dilution, the enthalpy of mixing was taken to be zero. Using calculated value of enthalpy of reaction (1) and available reference data on f H el (298.15 ) for constituents (Table 1) and sodium oxalate (1322.3 10 kJ/mol) [13], the standard enthalpy of formation of the studied mineral from ele ments was calculated using equation (16): f H el ( 298.15 K ) mineral = reaction(1) H +

crinitekyanoxalite series and pure oxalate kyanox alite determined in this work, we calculated f G el (298.15 ) for these minerals (Table 2). ACKNOWLEDGMENTS We are grateful to A.A. Mukhanova for help in determination of the chemical composition of the mineral. The work was supported by the Russian Founda tion for Basic Research (project nos. 07 05 00130 a, 08 05 00077 a, and 09 05 91330 NNIO_a) and a grant of the President of the Russian Federation o (project no. NSH 863.2008.5) and Foundation for Support of Russian Science (I.V.P.) REFERENCES
1. L. P. Ogorodova, L. V. Melchakova, M. F. Vigasina, et al., Cancrinite and Cancrisilite in the KhibinaLovozero Alkaline Complex: Thermochemical and Thermal Data, Geokhimiya 3, 260267 (2009) [Geochem. Int. 47, 260 267 (2009)]. 2. E. Bonaccorsi and S. Merlino, Modular Microporous Minerals: Cancrinite Davyne and CHS Phases, Rev. Mineral. Geochem. 57, 448449 (2005). 3. N. V. Chukanov, I. V. Pekov, L. V. Olysych, et al., Kyan oxalite, A New Mineral of Cancrinite Group with Oxalate Out of Framework Anion from the Lovozero Alkaline Massif (Kola Peninsula), Zap. Mineral. O va 138 (6), 1835. 4. H. H. Moenke, Mineralspektren. B. 2 (Akad. Verlag, Ber lin, 1962). 5. I. A. Kiseleva, L. P. Ogorodova, N. D. Topor, and O. G. Chigareva, Thermochemical Study of the CaOMgOSiO2 System, Geokhimiya, No. 12, 18111825 (1979). 6. B. J. Wood and O. J. Kleppa, Thermochemistry of ForsteriteFayalite Olivine Solutions, Geochim. Cosmochim. Acta 45, 529534 (1981). 7. R. A. Robie and B. S. Hemingway, Thermodynamic Properties of Minerals and Related Substances at 298.15 K and 1 Bar (105 Pascals) Pressure and at Higher Temper atures, U.S. Geol. Surv. Bull, No. 2131, 461 (1995). 8. I. A. Kiseleva, A. Navrotsky, I. A. Belitsky, and B. A. Fur senko, Thermochemical Study of Calcium Zeolites Heulandite and Stilbite, Am. Mineral 86, 448455 (2001).
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where i are the stoichiometric coefficients in equa tion (1). Obtained value (14473 21 kJ/mol) is the first determination of the enthalpy of formation of natural oxalate bearing mineral of the cancrinite group. This value is almost similar to the enthalpy of formation of proper cancrinite (Na6.93Ca0.545K0.01)[(Si6.47Al5.48Fe0.05)24](CO3)1.25 2.30H2O (14490 16 kJ/mol) determined by us [1], which confirms the validity of obtained values. On the basis of obtained calorimetric data for the intermediate member of the cancrinitekyanoxalite series, we calculated the enthalpy of formation of pure oxalate kyanoxalite Na7Si6Al624(C2O4)0.5 5H2O. For this purpose, experimental data on mineral studied in this work were recalculated for molecular mass of kyanoxalite (m.m. = 1009.41 g/mol). Value (298.15 K) calculated using equations (11) and f H el (16) from corrected calorimetric data for pure oxalate (ideal kyanoxalite) is listed in Table 2. In order to calculate the Gibbs free energies of the formation of the intermediate member of the cancrin itekyanoxalite series and pure oxalate kyanoxalite from elements, the unknown value of standard entropy was estimated on the basis of additive scheme from the average values of entropies for cations and anions in solid matters. Data on entropies of cations and anions required for calculations were taken from [14], and data on entropy contribution of zeolite water were taken from [15]. Absent value of entropy contribution for oxalate ion was calculated using data on S(298.15 K) [14] for lead oxalate. Using thus determined values of standard entropy and enthalpies of formation of intermediate member of the can

v H ( 298.15
i f el

K ) comp i ,

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THERMAL EVOLUTION AND THERMOCHEMISTRY OF THE CANCRINITE GROUP 9. L. P. Ogorodova, L. V. Melchakova, I. A. Kiseleva, and I. A. Belitsky, Thermochemical Study of Natural Pollu cite, Thermochim. Acta 403, 251256 (2003). 10. A. R. Kotelnikov, Yu. K. Kabalov, T. N. Zezyulya, et al., Experimental Study of CelestiteBarite Solid Solution, Geokhimiya, No. 12, 12861293 (2000) [Geochem. Int. 38, 11811187 (2000)]. 11. I. A. Kiseleva and L. P. Ogorodova, About Use of High Temperature Dissolution Calorimetry for the Determina tion of the Enthalpy of Formation of Hydroxyl Bearing Minerals by the Example of Talc and Tremolite, Geokhimiya, No. 12, 17451755 (1983). 12. I. A. Kiseleva, A. R. Kotelnikov, K. V. Martynov, et al., Thermodynamic Properties of Strontianite Witherite

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Solid Solution (Sr,Ba)CO3, Phys. Chem. Minerals 21, 392400 (1994). 13. E. G. Lavut and N. V. Chelovskaya, Design and Testing of a Hybrid of Isoperibol and Phase Change Calorimeters for Measurements of the Enthalpies of Reactions Requir ing Prolonged Heating, J. Chem Thermodyn. 27 (1995). 14. G. B. Naumov, B. N. Ryzhenko, and I. L. Khodakovskii, Reference Book on Thermodynamic Values (for Geologists) (Atomzidat, Moscow, 1971) [in Russian]. 15. G. K. Johnson, I. R. Tasker, H. E. Flotow, et al., Ther modynamic Studies of Mordenite, Dehydrated Morden ite, and Gibbsite, Am. Mineral. 77, 8593 (1992).

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