Structural Features and Thermal Behavior of Ion-Exchanged Clinoptilolite from Beli Plast Deposit (Bulgaria)
Abstract
:1. Introduction
2. Materials and Methods
3. Results and Discussion
3.1. PXRD Analysis
3.2. EDS SEM
3.3. Thermal Analyses
3.4. Rietveld Analysis
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Samples Oxides | Purified Natural-cpt | Na-cpt | K-cpt | Ca-cpt | Mg-cpt | Cd-cpt |
---|---|---|---|---|---|---|
SiO2 | 66.21 | 66.91 | 66.47 | 66.03 | 65.32 | 62.07 |
Al2O3 | 11.94 | 12.05 | 12.11 | 11.81 | 11.91 | 11.18 |
MgO | 0.74 | 0.49 | 0.49 | 0.43 | 2.76 | 0.30 |
CaO | 3.68 | 0.66 | 0.51 | 5.20 | 1.81 | 1.19 |
Na2O | 1.16 | 5.48 | 0.24 | 0.38 | 0.27 | 0.24 |
K2O | 1.94 | 0.59 | 8.70 | 0.34 | 0.96 | 0.64 |
CdO | – | – | – | – | – | 9.1 |
Fe2O3 | 0.21 | 0.17 | 0.15 | 0.16 | 0.17 | 0.18 |
H2O | 13.8 | 13.3 | 11.0 | 15.5 | 16.6 | 14.9 |
Σ | 99.68 | 99.65 | 99.67 | 99.85 | 99.80 | 99.80 |
Atoms per formula unit (apfu) | ||||||
Si | 29.61 | 29.66 | 29.62 | 29.73 | 29.59 | 29.65 |
Al | 6.29 | 6.29 | 6.36 | 6.27 | 6.37 | 6.29 |
Mg | 0.49 | 0.32 | 0.33 | 0.29 | 1.87 | 0.21 |
Ca | 1.76 | 0.31 | 0.24 | 2.51 | 0.88 | 0.61 |
Na | 1.01 | 4.71 | 0.21 | 0.33 | 0.24 | 0.22 |
K | 1.11 | 0.33 | 4.95 | 0.20 | 0.56 | 0.39 |
Cd | – | – | – | – | – | 2.03 |
Fe | 0.04 | 0.10 | 0.05 | 0.05 | 0.06 | 0.06 |
H2O | 21.05 | 20.19 | 16.83 | 23.49 | 25.40 | 24.02 |
Sample | Total Mass Loss, % | Total H2O Molecules | Evolved H2O Molecules in Low-Temperature Region | Endotherm Minima Temperature, °C |
---|---|---|---|---|
Natural-cpt | 13.8 | 20.6 | 12.4 up to 230 °C | 100.8 |
K-cpt | 11.0 | 16.4 | 8.8 up to 210 °C | 77.9 |
Na-cpt | 13.3 | 19.6 | 11.0 up to 220 °C | 85.8 |
Ca-cpt | 15.5 | 23.3 | 14.5 up to 250 °C | 96.1; 103.2 |
Mg-cpt | 16.6 | 25.0 | 16.8 up to 230 °C | 80.5; 104.0 |
Cd-cpt | 14.9 | 23.7 | 13.1 up to 230 °C | 115.0 |
Cations | Ionic Radii (Å) | Ionization Potential (eV) |
---|---|---|
K+ | 1.37 | 5.13 |
Na+ | 0.99 | 4.34 |
Ca2+ | 1.00 | 6.11 |
Mg2+ | 0.57 | 7.64 |
Cd2+ | 0.78 | 8.99 |
Natural-cpt | Na-cpt | Ca-cpt | K-cpt | Mg-cpt | Cd-cpt | |
---|---|---|---|---|---|---|
Rexp | 8.75 | 6.39 | 6.44 | 4.97 | 6.10 | 4.99 |
Rwp | 7.33 | 9.45 | 8.84 | 6.16 | 9.20 | 6.14 |
Rp | 6.69 | 7.45 | 6.94 | 4.62 | 7.17 | 4.80 |
GoF | 1.78 | 1.48 | 1.37 | 1.24 | 1.51 | 1.22 |
RB | 3.21 | 2.27 | 2.30 | 1.03 | 2.86 | 1.41 |
a (Å) | 17.6777 (8) | 17.6912 (7) | 17.6706 (9) | 17.6838 (9) | 17.6991 (7) | 17.6807 (8) |
b (Å) | 17.9485 (1) | 17.9453 (6) | 17.9374 (8) | 17.9898 (8) | 17.9957 (8) | 17.9919 (8) |
c (Å) | 7.4146 (4) | 7.4217 (3) | 7.4128 (4) | 7.4151 (4) | 7.4342 (3) | 7.4155 (4) |
β (°) | 116.377 (2) | 116.260 (2) | 116.370 (3) | 116.272 (3) | 116.274 (3) | 116.263 (3) |
V (Å3) | 2108.4 (2) | 2113.04 (2) | 2105.12 (23) | 2115.3 (2) | 2123.22 (3) | 2115.4 (3) |
Sites | Nat-cpt | K-cpt | Na-cpt | Ca-cpt | Mg-cpt | Cd-cpt |
---|---|---|---|---|---|---|
Na1 | 1.01 | 0.22 | 2.79 | 0.32 | 0.32 | 0.28 |
Na2 | 1.82 | |||||
K1 | 0.39 | |||||
K2 | 0.68 | |||||
K3 | 1.11 | 3.17 | 0.35 | 0.24 | 0.41 | 0.36 |
Ca1 | 0.65 | |||||
Ca2 | 1.77 | 0.78 | 0.28 | 1.86 | 1.00 | 0.68 |
Mg | 0.46 | 0.26 | 0.29 | 0.31 | 1.82 | |
Cd | 0.80 | |||||
Cd1 | 0.18 | |||||
Cd2 | 0.89 | |||||
Cd3 | 0.26 | |||||
Total Cd | 2.13 | |||||
O11 | 2.08 | 1.66 | 3.21 | 3.02 | 2.51 | 1.52 |
O12 | 1.59 | 1.32 | 2.24 | 2.00 | 2.80 | 0.66 |
O13 | 7.12 | 5.77 | 5.28 | 6.55 | 4.60 | 4.58 |
O14 | 2 | 2 | 2 | 2 | 2 | 1.0 |
O15 | 2.75 | 1.49 | 2.82 | 1.94 | 2.12 | 1.80 |
O16 | 2.56 | 3.16 | 2.00 | 1.95 | 1.05 | 2.16 |
O17 | 0.09 | 1.64 | 0.24 | - | 1.64 | 2.70 |
O18 | 1.09 | 2.07 | 2.96 | |||
O19 | 0.72 | |||||
Total H2O | 18.19 | 17.01 | 17.80 | 18.55 | 19.90 | 16.85 |
Samples | Cation Positions | Distance between Cations and H2O Molecules Å | ||||||||
---|---|---|---|---|---|---|---|---|---|---|
O11 | O12 | O13×4 | O14 | O15×2 | O16 | O17 | O18 | O19 | ||
Natural-cpt | Na | 2.63 | 2.40 * | 2.96 | 2.65 | |||||
Ca | 2.38 */2.63 | 2.55 * | ||||||||
K | 2.93 | |||||||||
Mg | 1.97 * | |||||||||
K-cpt | K1 | 2.81 * | ||||||||
K2 | 2.82 * | |||||||||
K3 | 2.94 * | 3.06 * | ||||||||
Ca | ||||||||||
Mg | ||||||||||
Na-cpt | Na1 | 2.62 | 2.40 * | 2.57 | 2.65 | |||||
Na2 | 2.43 */2.66 | 2.52 * | ||||||||
Ca2 | 2.38 */2.63 | 2.55 * | ||||||||
K | 2.93 | |||||||||
Mg | 1.94 | 2.15 * | ||||||||
Ca-cpt | Ca1 | 2.61 | 2.44 * | 2.56 | 2.60 | |||||
Ca2 | 2.39 */2.64 | 2.55 * | ||||||||
Na | 2.48 * | 2.58 | 2.60 | |||||||
K | 2.97 | |||||||||
Mg | 1.94 | 2.15 * | ||||||||
Mg-cpt | Mg | 2.32 * | 1.96 * | 1.75 | 2.15 * | 2.38 | ||||
Ca | 2.39 */2.64 | 2.55 * | ||||||||
Na | 2.61 | 2.79 | 2.99 | 2.51 * | ||||||
Cd-cpt | CdM4 | 2.12 * | 2.16 * | 2.30 * | ||||||
Cd2 | 2.24 * | 2.06 * | ||||||||
Cd3 | 2.17 * | 2.34 * | 2.39 * | |||||||
Cd1 | 2.25 * | 2.30 * | 2.33 * | |||||||
Na | 2.51 | |||||||||
Ca | 2.46 */2.51 * | 2.72 * |
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Dimowa, L.; Petrova, N.; Tzvetanova, Y.; Petrov, O.; Piroeva, I. Structural Features and Thermal Behavior of Ion-Exchanged Clinoptilolite from Beli Plast Deposit (Bulgaria). Minerals 2022, 12, 1576. https://doi.org/10.3390/min12121576
Dimowa L, Petrova N, Tzvetanova Y, Petrov O, Piroeva I. Structural Features and Thermal Behavior of Ion-Exchanged Clinoptilolite from Beli Plast Deposit (Bulgaria). Minerals. 2022; 12(12):1576. https://doi.org/10.3390/min12121576
Chicago/Turabian StyleDimowa, Louiza, Nadia Petrova, Yana Tzvetanova, Ognyan Petrov, and Iskra Piroeva. 2022. "Structural Features and Thermal Behavior of Ion-Exchanged Clinoptilolite from Beli Plast Deposit (Bulgaria)" Minerals 12, no. 12: 1576. https://doi.org/10.3390/min12121576