Földvári Mária
Handbook of thermogravimetric system of minerals and its use in geological practice
CONTENTS, PREFACE
Contents
INDEX OF FIGURES
INDEX OF TABLES
PREFACE
MEASUREMENT METHODS AND SYSTEM OF THERMAL REACTION OF MINERALS
INTRODUCTION TO THE THERMOANALYTICAL METHODS
Thermoanalytical techniques
Differential Thermal Analysis (DTA)
Thermogravimetry (TG)
Evolved Gas Analysis (EGA)
Derivative technique
Multiple techniques
Experimental conditions
Thermoanalytical parameters
Nomenclature of DTA and TG curves
Description of the shape of thermoanalytical curves (DTA, DTG)
Calibration
Temperature and DTA calibration
Evaluation of DTA peak resolution
Other materials usually used for calibration
Heat of reaction (ΔH)
TG calibration
DTG calibration
Effects influencing thermoanalytical curves
Standardization
Recommendations of ICTA Nomenclature Committee for reporting Thermal Analysis results
THERMOGRAVIMETRIC INVESTIGATION TECHNIQUES AND METHODS
Techniques
Quantitative determination based on mass-change
Derivative Thermogravimetry (DTG, DDTG)
Sample controlled Thermal Analysis (or controlled rate Thermal Analysis)
Coupled simultaneous techniques, EGA methods
Methods
Calculation of virtual kinetic parameters
Corrected decomposition temperature
Supplementary methods
CHARACTERISTIC THERMAL REACTIONS OF MINERAL GROUPS
Thermal activity of minerals
System of thermal decomposition reactions
Water in minerals. Dehydration
Adsorbed water
Water found in completely confined internal spaces
Water bound in solid solution
Crystal hydrates (constitutional water in water-bearing carbonate, sulphate, phosphate and salt minerals)
Thermal dissociation
Other thermal reactions with mass change (sublimation, oxidation, reduction)
Other thermal reactions without mass change
Solid-phase structural decomposition
Polymorphic transition
Melting
Curie point
Solid phase reaction
THERMOGRAVIMETRIC CURVES AND THEIR INTERPRETATION BY STOICHIOMETRIC PROCESSES OF MINERALS
1. Native elements
1.1. Sulphur: S
1.2. Graphite C
1.2.1. Analysis in air
1.2.2. Analysis in oxygen
2. Sulphides
2.1. Pyrite FeS2
2.2. Cinnabar HgS
2.3. Galena PbS
2.4. Sphalerite ZnS
2.5. Other chalcogenide minerals
3. Oxides
3.1. Silica minerals
3.1.1. Quartz SiO2
3.1.2. Opal SiO2·nH2O
3.1.3. Other silica minerals
3.2. Iron oxides
3.2.1. Magnetite Fe3O4
3.2.2. Hematite Fe2O3
3.2.3. "Ferrihydrite" Fe3+4-5(OH, O)12(2.5Fe2O3·4.5H2O or Fe5HO8·4H2O)
3.3. Manganese oxides
3.3.1. Pyrolusite MnO2
3.3.2. Other manganese oxides
3.4. Other oxides
4. Hydroxides
4.1. Simple hydroxides
4.1.1. Gibbsite Al(OH)3
4.1.2. Nordstrandite Al(OH)3
4.1.3. Brucite Mg(OH)2
4.1.4. Portlandite Ca(OH)2
4.1.5. Other simple hydroxides
4.2. Oxides containing Hydroxyl (oxyde-hydroxides)
4.2.1. Goethite α-FeOOH
4.2.2. Lepidocrocite γ-FeOOH
4.2.3. Manganite γ-MnOOH
4.2.4. Boehmite γ-AlOOH
4.2.5. Diaspore α-AlOOH
4.2.6. Alumogel AlOOH+nH2O
4.3. Hydroxide containing multiple cations
4.3.1. Lithiophorite (Al,Li)(OH)2·MnO2
4.4. Other hydroxides
4.5. References for bauxite
5. Silicates
5.1. Phyllosilicates
5.1.1. The 1:1 layer type clay minerals
5.1.2. 2:1 layer type clay minerals
5.2. Nesosilicates
5.2.1. Topaz Al2SiO4(F,OH)2
5.2.2. Epidote Ca2(Fe3+,Al)Al2(SiO4)(Si2O7)O(OH)
5.2.3. Vesuvianite Ca10(Mg,Fe)2Al4(SiO4)5(Si2O7)2(OH,F)4
5.2.4. Zunyite Al13Si5O20(OH,F)18Cl
5.2.5. Katoite Ca3Al2(SiO4)3-Ca3Al2(OH)12
5.3. Sorosilicates (and Cyclosilicates)
5.3.1. Hemimorphite Zn4((Si2O7(OH)2·H2O)
5.3.2. Axinite Ca2(Fe2+, Mg, Mn)Al2BO3Si4O122(OH)
5.3.3. Tourmaline ((Na,Ca)(Li,Mg,Fe2+Al)3(Al,Fe3+)6(B3Si6O27(O,OH,F)4
5.4. Inosilicates
5.4.1. Amphiboles (Ca,Na,K)0-3[(Mg,Fe,Mn,Al,Ti)5-7(Si,Al)8O22(O,OH,F)2]
5.4.2. Charoite K5Ca8(Si6O15)2(Si2O7)Si4O9(OH,F)·3(H2O)
5.5. Tectosilicates
5.5.1. Zeolites
5.5.2. Other tectosilicates
6. Carbonates
6.1. Water free simple carbonates
6.1.1. Calcite CaCO3
6.1.2. Magnesite MgCO3
6.1.3. Rhodochrosite MnCO3
6.1.4. Siderite FeCO3
6.1.5. Cerussite PbCO3
6.2. Water free double carbonates
6.2.1. Dolomite MgCa(CO3)2
6.2.2. Huntite Mg3Ca(CO3)4
6.2.3. Ankerite (real) (Mg>Fe),Ca(CO3)2
6.2.4. Ferrous dolomite
6.2.5. Kutnahorite (real) generally (Mn>Mg,Ca,Fe),Ca(CO3)2
6.3. Waterfree carbonates without additional anions
6.3.1. Kalicinite KHCO3
6.3.2. Teschemacherite (NH4)HCO3
6.4. Waterfree carbonates with additional anions
6.4.1. Malachite Cu2(OH)2CO3
6.4.2. Azurite Cu3((OH)CO3)2
6.4.3. Dawsonite Na3Al(CO3)3·2Al(OH)3
6.5 Water-bearing carbonates
6.5.1. Nesquehonite MgCO3·3H2O or Mg(HCO3)(OH)·2(H2O)
6.5.2. Hydromagnesite 3MgCO3·Mg(OH)2·3H2O
6.5.3. Dypingite Mg5(CO3)4(OH)2·5H2O
6.5.4. Hydrotalcite Mg6Al2(CO3)(OH)16·4(H2O)
6.6. Other carbonates
7. Sulphates
7.1. Waterfree sulfates
7.1.1. Mascagnite (NH4)2SO4
7.2. Water-bearing sulfates with mono cation
7.2.1. Chalcanthite CuSO4·5H2O
7.2.2. Melanterite FeSO4·7H2O
7.2.3. Rozenite FeSO4·4H2O
7.2.4. Szomolnokite FeSO4·H2O
7.2.5. Alunogen Al2(SO4)3·17H2O
7.2.6. Hexahydrite MgSO4·6H2O
7.2.7. Gypsum CaSO4·2H2O
7.3. Water-bearing sulfates with several different cations
7.3.1. Römerite Fe2+Fe3+2(SO4)4×14H2O
7.3.2. Voltaite K2Fe2+5Fe3+3Al(SO4)12·18(H2O)
7.3.3. Halotrichite Fe2+Al2(SO4)4·22(H2O)
7.3.4. Potassium-alum KAl(SO4)2·12H2O
7.3.5. Tschermigite (NH4)Al(SO4)2·12H2O
7.4. Waterfree sulfates with additional anions
7.4.1. Alunite KAl3(SO4)2(OH)6
7.4.2. Jarosite KFe3(SO4)2(OH)6
7.5. Water-bearing sulfates with additional anions
7.5.1. Aluminite Al2(SO4)(OH)4·7H2O
7.5.2. Fibroferrite Fe3+(SO4)(OH)·5H2O
7.5.3. Copiapite (Fe2+, Mg)(Fe3+,Al)4(SO4)6(OH)2·20H2O
8. Phosphates, arsenates, vanadates
8.1. Hydrated phosphates
8.1.1. Vivianite Fe2+3(PO4)2·8H2O
8.2. Anhydrous phosphates containing hydroxyl
8.2.1. Lazulite (Mg,Fe)Al2(PO4)2(OH)2
8.2.2. Gorceixite BaAl3(PO4)(PO3OH)(OH)6
8.3. Water-bearing phosphates with additional anions
8.3.1. Diadochite Fe3+2(PO4)(SO4)(OH)·6H2O
8.4. Hydrated arsenates
8.4.1. Kaňkite Fe3+AsO4·3.5H2O
9. Borates
10. Halides
10.1. Halite NaCl
10.2. Bischofite MgCl2·6H2O
11. Organic minerals
11.1. Whewellite Ca(C2O4)·H2O (calcium oxalate monohydrate)
11.2. Humboldtine (Oxalite) Fe2+(C2O4)·2H2O
12. Organic materials
12.1. Determination of the coalification of organic matter content of the sample
12.2. Proximate (immediate) analysis of coal
13. Investigation of rocks
13.1. Perlite
13.2. Phase analysis
14. Special geological applications
REFERENCES
MINERAL AND ROCK INDEXES
Preface
Thermal analysis plays a specific role in the identification and quantitative determination of mineral components of rocks. In spite of the fact that minerals were the first group of materials studied regularly by using thermoanalytical methods, the potential offered by these methods is still not fully utilized in the field of earth sciences. The range of thermoanalytical methods applied in earth sciences is rather wide. Most works are based on DTA. DTA data provide indirect analytical information on a material and the quantification of a reaction is limited. From quantitative phase analysis point of view it is very important that thermogravimetric measurements give direct and absolute values for thermal reactions making stoichiometric calculation possible. Both DTA (Differential Thermal Analysis) and TG (Thermogravimetry) are undoubtedly the most widespread methods, whereas the rest are normally applied rather occasionally, to find solution to specific problems only.
Thermogravimetry dates back to the work of Talabot who in 1833 equipped a laboratory with thermobalances for quality control of Chinese silk. Thermogravimetric analysis of the minerals and rocks has been applied systematically since the mid 1960s. Derivatography, the technique of simultaneous thermal analytical measurement developed by Pauliks was a combination of TG and DTA. The measure the rate of change of the sample property with temperature, later the sample controlled thermal analysis or controlled rate thermal analysis (quasi-thermogravimetry) and the computerized new generation of these equipments received the possibility to the author during 40 years to analyze about 30 000 geological samples. The experiences of this long time permit of the systematization of the thermal reactions of the minerals and made reasonable the compilation of this book. Handbook for geological samples based on thermogravimetry earlier only the otherwise excellent publication by Todor in 1972.
Mária Földvári