“…Melting temperatures used in the calculation were taken from the literature: 2023 K for CsAlSiO 4 , 46 2173 K for CsAlSi 2 O 6 , 47 and 1693 K for CsAlSi 5 O 12 . 48 The heat capacity at 298.2 K ( C p,298 ) of CsAlSi 2 O 6 was reported in the literature (173.2 J mol –1 K –1 ) 39,40 and the corresponding values for CsAlSiO 4 and CsAlSi 5 O 12 were estimated to be 121.9 and 299.6 J mol –1 K –1 respectively, from the Neumann–Kopp rule (simple stoichiometric summation of the C p,298 values of Cs 2 O, Al 2 O 3 , SiO 2 ).cWe shifted the estimated standard enthalpy of CsAlSiO 4 (−2121 by Lindemer 41 and −2133 kJ mol −1 by Taylor 42 ) and CsAlSi 5 O 12 by Lindemer 41 (−5805 kJ mol −1 ) to better reproduce the melting temperatures, as well as to obtain the plausible high temperature behaviors of Cs.d C p , Δ f H °, and S ° for gases were estimated using the statistical equations in ref (49) or (50), and the details are presented in the Supporting Information. The thermodynamic properties for elemental Cs, O atom, and O 2 molecule were cited from the NIST database.…”
Following
the nuclear accident at the Fukushima Daiichi Nuclear
Power Plant in 2011, even the municipal solid waste (MSW) and sewage
sludge (SS) in northeastern Japan became contaminated by radioactive
nuclides such as
137
Cs and
134
Cs. To understand
the state of radioactive cesium (r-Cs) in the incineration residues
of the municipal wastes, research groups studied the concentration
and the chemical form of r-Cs in the residues, as well as its water-leaching
behavior. In the present study, we conducted thermodynamic equilibrium
calculations to estimate the possible chemical forms of r-Cs in the
incineration residues. Thermodynamic data for cesium oxides and aluminosilicates
were collected and compiled into a new database to perform equilibrium
calculations for systems that include Cs. The calculation results
suggested that Cs (radiocesium and stable cesium) in municipal solid
waste was transformed into gaseous CsCl or crystalline aluminosilicate
at incineration temperatures and, when a molten aluminosilicate phase
(i.e., slag phase) was generated, a proportion of the Cs species was
dissolved into the slag phase. In the case of sewage sludge, Cs was
calculated to be transformed mostly into crystalline aluminosilicate
at incineration temperatures, whereas by analogy with the behaviors
of Na and K, Ca,Cs-phosphate double salts were also potential incineration
products. These results could account for the high leaching rates
of r-Cs from the MSW incineration fly ash and the low leaching rates
from the MSW incineration bottom ash and SS incineration fly ash reported
in earlier studies. In the case of dewatered SS that included a large
amount of slaked lime as a flocculant, it was exceptionally difficult
for the calculation to represent the fate of Cs, and we needed to
include the contribution of silica sand in a fluidized-bed combustor
in the equilibrium calculation to represent the low leaching rates
of alkali species from the dewatered SS fly ash. From the results
of the thermodynamic equilibrium calculations and also from the calculated
standard Gibbs energy of cesium aluminosilicate formation/decomposition
reactions, the effects of waste composition and incineration temperature
on the fate of Cs were examined: High incineration temperature and
large amounts of Ca and Cl in the waste composition increased the
fraction of gaseous CsCl in the furnace and thus resulted in the high
distribution ratios of Cs in the fly ash of MSW and the high leaching
rates of Cs from the fly ash.
“…Melting temperatures used in the calculation were taken from the literature: 2023 K for CsAlSiO 4 , 46 2173 K for CsAlSi 2 O 6 , 47 and 1693 K for CsAlSi 5 O 12 . 48 The heat capacity at 298.2 K ( C p,298 ) of CsAlSi 2 O 6 was reported in the literature (173.2 J mol –1 K –1 ) 39,40 and the corresponding values for CsAlSiO 4 and CsAlSi 5 O 12 were estimated to be 121.9 and 299.6 J mol –1 K –1 respectively, from the Neumann–Kopp rule (simple stoichiometric summation of the C p,298 values of Cs 2 O, Al 2 O 3 , SiO 2 ).cWe shifted the estimated standard enthalpy of CsAlSiO 4 (−2121 by Lindemer 41 and −2133 kJ mol −1 by Taylor 42 ) and CsAlSi 5 O 12 by Lindemer 41 (−5805 kJ mol −1 ) to better reproduce the melting temperatures, as well as to obtain the plausible high temperature behaviors of Cs.d C p , Δ f H °, and S ° for gases were estimated using the statistical equations in ref (49) or (50), and the details are presented in the Supporting Information. The thermodynamic properties for elemental Cs, O atom, and O 2 molecule were cited from the NIST database.…”
Following
the nuclear accident at the Fukushima Daiichi Nuclear
Power Plant in 2011, even the municipal solid waste (MSW) and sewage
sludge (SS) in northeastern Japan became contaminated by radioactive
nuclides such as
137
Cs and
134
Cs. To understand
the state of radioactive cesium (r-Cs) in the incineration residues
of the municipal wastes, research groups studied the concentration
and the chemical form of r-Cs in the residues, as well as its water-leaching
behavior. In the present study, we conducted thermodynamic equilibrium
calculations to estimate the possible chemical forms of r-Cs in the
incineration residues. Thermodynamic data for cesium oxides and aluminosilicates
were collected and compiled into a new database to perform equilibrium
calculations for systems that include Cs. The calculation results
suggested that Cs (radiocesium and stable cesium) in municipal solid
waste was transformed into gaseous CsCl or crystalline aluminosilicate
at incineration temperatures and, when a molten aluminosilicate phase
(i.e., slag phase) was generated, a proportion of the Cs species was
dissolved into the slag phase. In the case of sewage sludge, Cs was
calculated to be transformed mostly into crystalline aluminosilicate
at incineration temperatures, whereas by analogy with the behaviors
of Na and K, Ca,Cs-phosphate double salts were also potential incineration
products. These results could account for the high leaching rates
of r-Cs from the MSW incineration fly ash and the low leaching rates
from the MSW incineration bottom ash and SS incineration fly ash reported
in earlier studies. In the case of dewatered SS that included a large
amount of slaked lime as a flocculant, it was exceptionally difficult
for the calculation to represent the fate of Cs, and we needed to
include the contribution of silica sand in a fluidized-bed combustor
in the equilibrium calculation to represent the low leaching rates
of alkali species from the dewatered SS fly ash. From the results
of the thermodynamic equilibrium calculations and also from the calculated
standard Gibbs energy of cesium aluminosilicate formation/decomposition
reactions, the effects of waste composition and incineration temperature
on the fate of Cs were examined: High incineration temperature and
large amounts of Ca and Cl in the waste composition increased the
fraction of gaseous CsCl in the furnace and thus resulted in the high
distribution ratios of Cs in the fly ash of MSW and the high leaching
rates of Cs from the fly ash.
“…(Kiseleva et al, 2001). в Справочные данные (Robie, Hemingway, 1995 (Ogorodova et al, 2003); е (Киселева и др., 1979); ж (Westrich, Navrotsky, 1981 Для расчета значений энергии Гиббса образования апофиллитов из элементов были оценены отсутствующие в литературе величины их стандартных энтропий (табл. 3).…”
Thermochemical study of natural minerals of the apophyllite group: fluorapophyllite-(K) KCa4[Si8O20]F . 8H2O (Maharashtra, India) (I) and hydroxylapophyllite-(K) KCa4[Si8O20]OH . 8H2O (Norilsk, Russia) (II) were performed on a high-temperature heat-flux microcalorimeter Tian–Calvet “Setaram” (France) using the melt solution calorimetry method. The first data on the enthalpies of formation from the elements for the minerals studied are obtained: -13 205±13 kJ/mol (I) and -13 054±20 kJ/mol (II). The values of their standard entropies and Gibbs energies of formation are estimated.
“…c Calculated using the reference data on [H 0 (973 K)-H 0 (298.15 K)] (Robie and Hemingway 1995) and experimental data on D sol H 0 (973 K) according to Kiseleva et al (1979). d Calculated using the reference data on [H 0 (973 K)-H 0 (298.15 K)] (Robie and Hemingway 1995) and experimental data on D sol H 0 (973 K) according to Ogorodova et al (2003). e Calculated using the reference data on [H 0 (973 K)-H 0 (298.15 K)] (Robie and Hemingway 1995) and experimental data on D sol H 0 (973 K) according to Kiseleva (1976).…”
This paper presents the results of the first experimental thermochemical investigation of two natural trioctahedral chlorites (clinochlores). The study was performed with the help of a high-temperature heat-flux Tian-Calvet microcalorimeter. The samples were characterized by X-ray spectroscopy analysis, X-ray powder diffraction, thermal analysis, and FTIR spectroscopy. The enthalpies of formation of clinochlores were found using the melt solution calorimetry method to be: -8806 ± 16 kJ/mol for composition (Mg 4.9 Fe 2+ 0.3 Al 0.8 )[Si 3.2 Al 0.8 O 10 ](OH) 8 and -8748 ± 24 kJ/mol for composition (Mg 4.2 Fe 2+ 0.6 Al 1.2 ) [Si 2.8 Al 1.2 O 10 ](OH) 8 . The experimental data for natural samples allowed calculating the enthalpies of formation for end-members and intermediate members of the clinochlore (Mg 5 Al)[Si 3 AlO 10 ](OH) 8 and chamosite (Fe 5 Al)[Si 3 AlO 10 ](OH) 8 series. An important feature of the clinochlore structure is the presence of two distinct hydroxyl-containing octahedral layers: the interlayer octahedral sheet and octahedral 2:1 layer; the enthalpies of water removal from these positions in clinochlore structure were determined as: 53 ± 20 kJ/(mol·H 2 O) and 131 ± 10 kJ/(mol·H 2 O), respectively. These obtained first thermodynamic characteristics of Mg-Fe clinochlores can be used for quantitative thermodynamic modeling of geological and industrial processes including clinochlores of different composition.
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