Index of Figures ................................................ 7
Index of Tables ................................................ 11
Preface ........................................................ 13
Measurement methods and system of thermal reaction of
minerals ....................................................... 15
Introduction to the thermoanalytical methods ................... 16
Thermoanalytical techniques ................................. 16
Differential Thermal Analysis (DTA) ...................... 16
Thermogravimetry (TG) .................................... 17
Evolved Gas Analysis (EGA) ............................... 17
Derivative technique ..................................... 17
Multiple techniques ...................................... 17
Experimental conditions ..................................... 17
Thermoanalytical parameters ................................. 17
Nomenclature of DTA and TG curves ........................... 18
Description of the shape of thermoanalytical curves
(DTA, DTG) ............................................... 19
Calibration ................................................. 19
Temperature and DTA calibration .......................... 19
Evaluation of DTA peak resolution ........................ 20
Other materials usually used for calibration ............. 20
Heat of reaction (AH) ................................. 20
TG calibration ........................................ 20
DTG calibration ....................................... 20
Effects influencing thermoanalytical curves .............. 20
Standardization .......................................... 21
Recommendations of ICTA Nomenclature Committee for
reporting Thermal Analysis results ....................... 21
Thermogravimetric investigation techniques and methods ......... 22
Techniques .................................................. 22
Quantitative determination based on mass-change .......... 22
Derivative Thermogravimetry (DTG, DDTG) .................. 23
Sample controlled Thermal Analysis (or controlled rate
Thermal Analysis) ........................................ 23
Coupled simultaneous techniques, EGA methods ............. 24
Methods ..................................................... 25
Calculation of virtual kinetic parameters ................ 25
Corrected decomposition temperature ...................... 26
Supplementary methods ....................................... 27
Characteristic thermal reactions of mineral groups ............. 27
Thermal activity of minerals ................................ 27
System of thermal decomposition reactions ................... 28
Water in minerals. Dehydration .............................. 28
Adsorbed water ........................................... 29
Interlayer waters bond by phyllosilicates ............. 29
"Zeolitic water" ...................................... 36
Water in amorphous phases ............................. 36
Water found in completely confined internal spaces ....... 37
Water bound in solid solution ............................ 38
Crystal hydrates (constitutional water in water-bearing
carbonate, sulphate, phosphate and salt minerals) ........ 38
Thermal dissociation ........................................ 40
Other thermal reactions with mass change (sublimation,
oxidation, reduction) ....................................... 43
Other thermal reactions without mass change ................. 44
Solid-phase structural decomposition ..................... 44
Polymorphic transition ................................... 44
Melting .................................................. 45
Curie point .............................................. 45
Solid phase reaction ..................................... 46
Thermogravimetric curves and their interpretation by
stoichiometric processes of minerals ........................... 47
1 Native elements ............................................. 48
1.1 Sulphur: S ............................................. 48
1.2 Graphite С ............................................. 48
1.2.1 Analysis in air ................................. 48
1.2.2 Analysis in oxygen .............................. 49
2 Sulphides ................................................... 49
2.1 Pyrite FeS2 ............................................ 52
2.2 Cinnabar HgS ........................................... 53
2.3 Galena PbS ............................................. 54
2.4 Sphalerite ZnS ......................................... 54
2.5 Other chalcogenide minerals ............................ 54
3 Oxides ...................................................... 55
3.1 Silica minerals ........................................ 55
3.1.1 Quartz SiO2 ..................................... 55
3.1.2 Opal SiO2•nH2O .................................. 56
3.1.3 Other silica minerals ........................... 56
3.2 Iron oxides ............................................ 57
3.2.1 Magnetite Fe3O4 ................................. 57
3.2.2 Hematite Fe2O3 .................................. 57
3.2.3 "Ferrihydrite Fe3+4-55(OH, O)12(2.5Fe2O3•4.5H2O
or Fe5HO8•4H20)" ................................ 57
3.3 Manganese oxides ....................................... 60
3.3.1 Pyrolusite MnO2 ................................. 60
3.3.2 Other manganese oxides .......................... 60
3.4 Other oxides ........................................... 61
4 Hydroxides .................................................. 61
4.1 Simple hydroxides ...................................... 61
4.1.1 Gibbsite Al(OH)3 ................................ 61
4.1.2 Nordstrandite Al(OH)3 ........................... 62
4.1.3 Brucite Mg(OH)2 ................................. 63
4.1.4 Portlandite Ca(OH)2 ............................. 63
4.1.5 Other simple hydroxides ......................... 63
4.2 Oxides containing Hydroxyl (oxyde-hydroxides) .......... 64
4.2.1 Goethite α-FeOOH ................................ 64
4.2.2 Lepidocrocite γ-FeOOH ........................... 65
4.2.3 Manganite γ-MnOOH ............................... 65
4.2.4 Boehmite γ-АlOОН ................................ 66
4.2.5 Diaspore α-АlOОН ................................ 66
4.2.6 Alumogel AlOOH+nH2O ............................. 67
4.3 Hydroxide containing multiple cations .................. 67
4.3.1 Lithiophorite (Al,Li)(OH)2•MnO2 ................. 67
4.4 Other hydroxides ....................................... 67
4.5 References for bauxite ................................. 67
5 Silicates ................................................... 68
5.1 Phyllosilicates ........................................ 68
5.1.1 The 1:1 layer type clay minerals ................ 68
5.1.1.1 Kaolinite subgroup ..................... 68
5.1.1.1.1 Kaolinite (kaolinite-Tc)
Al2Si2O5(OH)4 .................... 68
5.1.1.1.2 Dickite (kaolinite-2M)
Al2Si2O5(OH)4 .................... 70
5.1.1.1.3 Fireclay (kaolinite-1Md)
Al2Si2O5(OH)4•nH20 (n<2) ......... 70
5.1.1.1.4 Halloysite
Al2Si2O5(OH)4•2H2O ............... 71
5.1.1.1.5 Allophane non-crystalline
mAl2O3•nSiO2•pH2O or Al2O3•
(SiO2)13-2•(H2O)25-3 .............. 71
5.1.1.2 Serpentine subgroup .................... 72
5.1.2 2:1 layer type clay minerals .................... 74
5.1.2.1 Pyrophyllite-Talc group ................ 75
5.1.2.1.1 Pyrophyllite
Al2Si4O10(OH)2 ................... 75
5.1.2.1.2 Talc Mg3Si4O10(OH)2 ......... 76
5.1.2.2 Smectite group ......................... 76
5.1.2.2.1 Montmorillonite
(Na,Ca)O3(Al,Mg)2Si4O10
(OH)2•n(H2O) ..................... 76
5.1.2.2.1.1 Ca-montmorillonite ........ 76
5.1.2.2.1.2 Na-montmorillonite ........ 78
5.1.2.2.1.3 "Abnormal
montmorillonites" ......... 78
5.1.2.2.2 Beidellite (Na,Ca)0.5Al2
(Si3.5Al0.5)O10(OH)2•n(H2O) ...... 80
5.1.2.2.3 Nontronite (Na,Ca)0.3Fe3+
2(Si,Al)4O10(OH)2•n(H2O) ........ 80
5.1.2.2.4 Saponite (Na,Ca)0.3(Mg,Fe2+)
3(Si,Al)4O10(OH)2•4(H2O) ........ 80
5.1.2.3 Vermiculite group (Mg,Fe2+,Al)3(Al,Si)
4O10(OH)2•n(H2O) ....................... 81
5.1.2.4 Mica group ............................. 82
5.1.2.4.1 Muscovite Kal2[AlSi3O10
(OH,F)2] ......................... 82
5.1.2.4.2 Biotite K(Mg,Fe2+)3
[AlSi3O10](OH,F)2 ................ 82
5.1.2.5 Hydromica (clay-mica, interlayer-
deficient mica) group .................. 83
5.1.2.5.1 Illite K0,65[Al,Mg,Fe]
2Al0.65Si3.35O10(OH)2H2O or
(K,H3O)Al2 (Si3Al)O10 (H2O,OH)2 .. 83
5.1.2.5.2 Hydromuscovite (sericite) ........ 84
5.1.2.5.3 Glauconite (K,Na)
(Fe3+,Al,Mg)2(Si,Al)4O10(OH)
2H2O ............................ 84
5.1.2.6 Chlorite group (2:1 layer with
interlayer hydroxide sheet/ or
2:l:l/or 2:2 layer type) ............... 85
5.1.2.7 Interstratified or mixed-layer
minerals ............................... 86
5.1.2.7.1 Regularly interstratified
minerals ......................... 86
5.1.2.7.1.1 Rectorite (1:1
interstratification
of dioctahedral
paragonitesmectite)
(Na,Ca)Al4(Si,Al)
8O20(OH)4•2H2O ............. 86
5.1.2.7.1.2 Tosudite (1:1
interstratification
of dioctahedral
chlorite-smectite) ......... 86
5.1.2.7.2 Randomly interstratified
minerals ......................... 87
5.1.2.7.2.1 Illite-montmorillonite .... 87
5.1.2.7.2.2 Chlorite-vermiculite ...... 87
5.1.2.7.2.3 Talc-saponite ............. 87
5.1.2.8 Pseudo-layer silicates ................. 88
5.1.2.8.1 Palygorskite [(Mg,Al,Fe)2Si4O10
(OH)•4H2O ........................ 88
5.1.2.8.2 Sepiolite Mg4Si6O15(OH)2•
6(H20) ........................... 89
5.1.2.9 Phyllosilicate two-dimensional
infinite sheets with other than six-
membered rings ........................ 89
5.1.2.9.1 Apophyllite KCa4(Si4O10)2(F,OH)•
8(H2O) ........................... 89
5.1.2.9.2 Prehnite Ca2Al2Si3O10(OH)2 ....... 90
5.1.2.9.3 Tobermorite Ca5(OH)2Si6O16•
4H2O ............................. 90
5.2 Nesosilicates .......................................... 91
5.2.1 Topaz Al2SiO4(F,OH)2 ............................ 91
5.2.2 Epidote Ca2(Fe3+,Al)Al2(SiO4)(Si2O7)O(OH) ....... 91
5.2.3 Vesuvianite Ca10(Mg,Fe)2Al4(SiO4)5(Si2O7)2
(OH,F)4 ......................................... 92
5.2.4 Zunyite Al13Si5O20(OH,F)18Cl .................... 92
5.2.5 Katoite Ca3Al2(SiO4)3-Ca3Al2(OH)12 .............. 93
5.3 Sorosilicates (and Cyclosilicates) ..................... 93
5.3.1 Hemimorphite Zn4((Si2O7(OH)2H20) ................ 93
5.3.2 Axinite Ca2(Fe2+,Mg, Mn)Al2BO3Si4O12(OH) ........ 93
5.3.3 Tourmaline ((Na,Ca)(Li,Mg,Fe2+Al)3(Al,Fe3+)6
(B3Si6O27(O,OH,F)4 .............................. 94
5.4 Inosilicates ........................................... 94
5.4.1 Amphiboles (Ca,Na,K)0-3[(Mg,Fe,Mn,Al,Ti)5-7
(Si,Al)8O22(O,OH,F)2] ........................... 94
5.4.2 Charoite K5Ca8(Si6O15)2(Si2O7)Si4O9(OH,F)•
3(H20) .......................................... 94
5.5 Tectosilicates ......................................... 95
5.5.1 Zeolites ........................................ 95
5.5.1.1 Zeolites with Chains of 4-membered
rings, Al2Si2O10 ....................... 95
5.5.1.1.1 Natrolite Na2[Al2Si3O10]•2H2O .... 95
5.5.1.1.2 Gonnardite (tetranatrolite)
(Na,Ca)6-8[(Al,Si)20O40]2H2O ..... 96
5.5.1.1.3 Mesolite Na2Ca2[Al6Si9O30]•8H2O .. 96
5.5.1.1.4 Thomsonite NaCa2[Al5Si5O20]•
6H2O ............................. 97
5.5.1.1.5 Scolecite Ca[Al2Si3O10]-3H2O ..... 98
5.5.1.1.6 Edingtonite Ba[Al2Si3O10]•4H2O ... 98
5.5.1.2 Zeolites with chains of single
connected 4-membered rings ............. 98
5.5.1.2.1 Analcime Na[AlSi2O6]H2O .......... 98
5.5.1.2.2 Laumontite Ca[Al2Si4O12]•4-
4.5H2O(fully hydrated laumontite) ...... 99
5.5.1.3 Zeolites with chains of double-
connected 4-membered rings ............ 100
5.5.1.3.1 Gismondine Ca[Al2Si2O8]•4.4-
4.5H20 .......................... 100
5.5.1.3.2 Phillipsite (K,Na,Ca)4
[(Si,Al)16O32]•12H2O ............ 100
5.5.1.3.3 Harmotome Ba2(Ca0.5Na)[Al6Si10
O32]•12H2O ...................... 101
5.5.1.4 Zeolites with chains of 5-membered
rings ................................. 101
5.5.1.4.1 Mordenite (Na,Ca,K)6
[AlSi5O12]8•28H2O ............... 101
5.5.1.5 Zeolites with sheets of 4-4-1-1
structural units ...................... 102
5.5.1.5.1 Heulandite (Ca,Na,K,Sr)9
[(Si,Al)36O72]Z•nH20 (n=22-26) .. 102
5.5.1.5.2 Clinoptilolite (K,Na,Ca)6
[(Si,Al)36O72]Z•nH20 (n=20-24) .. 103
5.5.1.5.3 Stilbite (Na,Ca)9[Si,Al)36O72]
•27-30 H20 ...................... 104
5.5.1.6 Zeolites with cages and double cages
of 4-, 6- and 8-membered rings ........ 104
5.5.1.6.1 Gmelinite Na8[Al8Si16O48]•
21.5H2O or K8[Al8Si16O48]•
23.5H20 or Ca4[Al8Si16O48]•
23.5H20 ......................... 104
5.5.1.6.2 Erionite Na10[Al10Si26O72]•
24.6H2O or K10[Al10Si26O72]•
32H2O or Ca5[Al10Si26O72]•
31H2O ........................... 105
5.5.1.6.3 Chabasite(Ca0.5,Na,K)4
[Al4Si8O24]•12H2O ............... 105
5.5.1.6.4 Faujasite (Na,Ca,Mg)2[(Si.
Al)12O24]•nH2O (n≈16) ........... 106
5.5.1.7 Thermoanalytical data of other
zeolites .............................. 106
5.5.2 Other tectosilicates ........................... 107
6 Carbonates ................................................. 107
6.1 Water free simple carbonates .......................... 107
6.1.1 Calcite CaCO3 .................................. 108
6.1.2 Magnesite MgCO3 ................................ 109
6.1.3 Rhodochrosite MnCO3 ............................ 109
6.1.4 Siderite FeCO3 ................................. 109
6.1.5 Cerussite PbCO3 ................................ 110
6.2 Water free double carbonates .......................... 111
6.2.1 Dolomite MgCa(CO3)2 ............................ 111
6.2.2 Huntite Mg3Ca(CO3)4 ..,......................... 113
6.2.3 Ankerite (real) (Mg>Fe),Ca(CO3)2 ............... 114
6.2.4 Ferrous dolomite ............................... 114
6.2.5 Kutnahorite (real) generally (Mn>Mg,Ca,Fe),
Ca(CO3)2 ....................................... 115
6.3 Waterfree carbonates without additional anions ........ 116
6.3.1 Kalicinite KHCO3 ............................... 116
6.3.2 Teschemacherite (NH4)HCO3 ...................... 116
6.4 Waterfree carbonates with additional anions ........... 117
6.4.1 Malachite Cu2(OH)2CO3 .......................... 117
6.4.2 Azurite Cu3((OH)CO3)2 .......................... 117
6.4.3 Dawsonite Na3Al(CO3)3•2Al(OH)3 ................. 117
6.5 Water-bearing carbonates ............................... 117
6.5.1 Nesquehonite MgCO3-3H2O or Mg(HCO3)(OH)-
2(H2O) ......................................... 117
6.5.2 Hydromagnesite 3MgCO3Mg(OH)2•3H2O .............. 118
6.5.3 Dypingite Mg5(CO3)4(OH)2•5H20 .................. 118
6.5.4 Hydrotalcite Mg6Al2(CO3)(OH)16•4(H2O) .......... 118
6.6 Other carbonates ...................................... 119
7 Sulphates .................................................. 121
7.1 Waterfree sulfates .................................... 122
7.1.1 Mascagnite (NH4)2SO4 ........................... 122
7.2 Water-bearing sulfates with mono cation ............... 122
7.2.1 Chalcanthite CuSO4-5H2O ........................ 122
7.2.2 Melanterite FeSO4-7H2O ......................... 123
7.2.3 Rozenite FeSO4-4H2O ............................ 123
7.2.4 Szomolnokite FeSO4H2O .......................... 124
7.2.5 Alunogen Al2(SO4)3•17H2O ....................... 124
7.2.6 Hexahydrite MgSO4-6H2O ......................... 124
7.2.7 Gypsum CaSO4•2H2O .............................. 125
7.3 Water-bearing sulfates with several different
cations ............................................... 125
7.3.1 Römerite Fe2+Fe3+2(SO4)4×l4H2O ................. 125
7.3.2 Voltaite K2Fe2+5Fe3+3Al(SO4)12•18(H20) .......... 126
7.3.3 Halotrichite Fe2+Al2(SO4)4•22(H2O) ............. 126
7.3.4 Potassium-alum KAl(SO4)2•12H2O ................. 126
7.3.5 Tschermigite (NH4)Al(SO4)2•12H2O ............... 127
7.4 Waterfree sulfates with additional anions ............. 127
7.4.1 Alunite Kal3(SO4)2(OH)6 ........................ 127
7.4.2 Jarosite KFe3(SO4)2(OH)6 ....................... 128
7.5 Water-bearing sulfates with additional anions ......... 128
7.5.1 Aluminite Al2(SO4)(OH)4•7H2O ................... 128
7.5.2 Fibroferrite Fe3+(SO4)(OH)-5H2O ................ 129
7.5.3 Copiapite (Fe2+, Mg)(Fe3+,Al)4(SO4)6(OH)2•
20H2O .......................................... 129
8 Phosphates, arsenates, vanadates ........................... 130
8.1 Hydrated phosphates ................................... 130
8.1.1 Vivianite Fe2+3(PO4)2-8H2O ..................... 130
8.2 Anhydrous phosphates containing hydroxyl .............. 130
8.2.1 Lazulite (Mg,Fe)Al2(PO4)2(OH)2 ................. 130
8.2.2 Gorceixite BaAl3(PO4)(PO3OH)(OH)6 .............. 131
8.3 Water-bearing phosphates with additional anions ....... 131
8.3.1. Diadochite Fe3+2(PO4)(SO4)(OH)•6H2O ............ 131
8.4 Hydrated arsenates .................................... 132
8.4.1. Kaňkite Fe3+AsO4•3.5H20 ........................ 132
9 Borates .................................................... 133
10 Halides .................................................... 133
10.1 Halite NaCl ........................................... 133
10.2 Bischofite MgCl2•6H20 ................................. 134
11 Organic minerals ........................................... 134
11.1 Whewellite Ca(C2O4)H2O (calcium oxalate
monohydrate) .......................................... 134
11.2 Humboldtine (Oxalite) Fe2+(C2O4)•2H2O ................. 134
12 Organic materials .......................................... 135
12.1 Determination of the coalification of organic matter
content of the sample ................................. 135
12.2 Proximate (immediate) analysis of coal ................ 135
13 Investigation of rocks ..................................... 136
13.1 Perlite ............................................... 136
13.2 Phase analysis ........................................ 137
14 Special geological applications ............................ 138
References ................................................. 141
Mineral and rock indexes ...................................... 177
|
