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Fluorine Calorimetry

ISBN:
1-56700-146-7 (印刷)

Fluorine Calorimetry

V. Ya. Leonidov
Glushko Thermocenter Russian Academy of Sciences, Moscow, Russia

P. A. G. O'Hare
Formerly of the National Institute of Standards and Technology, Gaithersburg, Maryland

説明

This book contains material, with analyses of the results obtained by fluorine combustion calorimetry over the past two decades and is devoted to problems that dominated the development of fluorine bomb calorimetry: purification and analysis of fluorine; methods devised for the combustion of different substances and analysis of the reaction products; construction of calorimetric bombs; peripheral apparatus for the safe manipulation of F2 and fluorides; and matters that address the treatment of experimental results of combustion of different substances in fluorine and other fluorine-containing oxidants.



261 pages, © 1999

目次:

Dedication
Foreword
Preface
1. Introduction
Thermochemistry. Enthalpies of chemical reactions
Some general information about calorimetry
About calorimetric investigations with fluorine: An historical perspective
Part One: Problems Associated with the Development of Fluorine Calorimetry
1. APPLICATION OF FLUORINE TO CALORIMETRY
1.1 MODIFICATIONS AND MAIN FEATURES OF FLUORINE CALORIMETRY
1.2 PROPERTIES OF FLUORINE. PURITY REQUIREMENTS FOR COMBUSTION CALORIMETRY
1.2.1 Characteristics of Elemental Fluorine
1.2.2 Physical and Chemical Properties of Fluorine
1.2.3 Manufacture of Fluorine
1.2.4 Requirements for Fluorine Used as a Reagent in Calorimetry
1.3 CONSTRUCTION AND PREPARATION OF APPARATUS FOR FLUORINE CALORIMETRY
1.3.1 Materials, Tanks, Tubing, and Accessories
1.3.2 Preparation and Passivation of the Apparatus
1.4 TECHNIQUES FOR THE COMBUSTION OF SUBSTANCES IN FLUORINE AND INVESTIGATION OF THE PRODUCTS OF REACTION
1.5 SAFETY CONSIDERATIONS FOR WORK WITH FLUORINE AND INORGANIC FLUORIDES
1.6 TREATMENT OF THE RESULTS OBTAINED BY FLUORINE CALORIMETRY
2. PURIFICATION AND ANALYSIS OF FLUORINE
2.1 Purification of Fluorine
2.2 Methods Used to Analyze Fluorine
2.3 Analysis of Fluorine: the Mercury Method
3. APPARATUS FOR CALORIMETRIC INVESTIGATIONS WITH FLUORINE
3.1 DESIGN OF CALORIMETRIC BOMBS FOR INVESTIGATIONS WITH FLUORINE
3.1.1 Single-Compartment Calorimetric Bombs
3.1.2 Two-Compartment Calorimetric Bombs
3.1.3 The Glass Reaction Vessel of Gross et al.
3.1.4 About the Heat Effect of Expanding Fluorine from One Chamber into Another
3.2 AUXILIARY APPARATUS
3.2.1 Glass Bombs for Test Combustions in Fluorine
3.2.2 Gas-Handling Systems for Fluorine Calorimetry
3.2.3 Procedures for the Analysis of Products of Fluorination
3.3 FLOW CALORIMETRY WITH FLUORINE
References to Part One
Part Two: Determination of Enthalpies of Formation of Substances by Fluorine Calorimetry
1. FLUORIDES OF METALS
1.1 ZIRCONIUM TETRAFLUORIDE (ZrF4)
1.2 TITANIUM TETRAFLUORIDE (TiF4)
1.3 HAFNIUM TETRAFLUORIDE (HfF4)
1.4 URANIUM HEXAFLUORIDE (UF6)
1.5 NIOBIUM PENTAFLUORIDE (NbF5)
1.6 TANTALUM PENTAFLUORIDE (TaF5)
1.7 RUTHENIUM PENTAFLUORIDE (RuF5)
1.8 CADMIUM DIFLUORIDE (CdF2)
1.9 ZINC DIFLUORIDE (ZnF2)
1.10 MAGNESIUM DIFLUORIDE (MgF2)
1.11 YTTRIUM TRIFLUORIDE (YF3)
1.12 NICKEL DIFLUORIDE (NiF2)
1.13 ALUMINUM TRIFLUORIDE (AlF3)
1.14 THORIUM TETRAFLUORIDE (ThF4)
1.15 COPPER DIFLUORIDE (CuF2)
1.16 BERYLLIUM DIFLUORIDE (BeF2)
1.17 MOLYBDENUM HEXAFLUORIDE (MoF6)
1.18 TUNGSTEN HEXAFLUORIDE (WF6)
1.19 VANADIUM PENTAFLUORIDE (VF5)
1.20 GERMANIUM TETRAFLUORIDE (GeF4)
1.21 ANTIMONY PENTAFLUORIDE (SbF5)
1.22 IRON (III) TRIFLUORIDE (FeF3)
1.23 PALLADIUM (II) HEXAFLUOROPALLADATE (IV) (Pd2F3)
1.24 RARE EARTH TRIFLUORIDES
1.25 SUMMARY
2. FLUORIDES OF NONMETALS
2.1 HYDROGEN FLUORIDE (HF)
2.2 BORON TRIFLUORIDE (BF3)
2.3 TETRAFLUOROMETHANE (CF4)
2.4 SILICON TETRAFLUORIDE (SiF4)
2.5 PHOSPHORUS PENTAFLUORIDE (PF5)
2.6 ARSENIC PENTAFLUORIDE (AsF5)
2.7 SULFUR HEXAFLUORIDE (SF6)
2.8 SELENIUM HEXAFLUORIDE (SeF6)
2.9 TELLURIUM HEXAFLUORIDE (TeF6)
2.10 BROMINE TRIFLUORIDE AND PENTAFLUORIDE (BrF3, BrF5)
2.11 CHLORINE MONOFLUORIDE (ClF)
2.12 IODINE FLUORIDES (IF5, IF7)
2.13 SUMMARY
3. COMPOUNDS
3.1 OXIDES
3.1.1 Boron Oxide (B2O3)
3.1.2 Silicon Dioxide (SiO2)
3.1.3 Germanium Dioxide (GeO2)
3.1.4 Uranium Dioxides (UO2 and UO2.023)
3.1.5 Nitrosyl Fluoride (NOF)
3.2 SULFIDES
3.2.1 Silicon Disulfide (SiS2)
3.2.2 Potassium Sulfide (K2S)
3.2.3 Titanium Sulfide (TiS2)
3.2.4 Germanium (II) Sulfide (GeS)
3.2.5 Germanium (IV) Disulfide (GeS2, cr and vit)
3.2.6 Arsenic Sulfides (As4S4 and As2S3)
3.2.7 Vanadium Monosulfide (VS1.043)
3.2.8 Molybdenum Disulfide (MoS2)
3.2.9 Antimony Sesquisulfide (Sb2S3)
3.2.10 Tungsten Disulfide (WS2)
3.2.11 Uranium Sulfides (US, US2)
3.3 NITRIDES
3.3.1 Boron Nitride (BN)
3.3.2 Silicon Nitride (Si3N4, cr, α- and β-)
3.3.3 Gallium Nitride (GaN)
3.3.4 Uranium Nitrides (UN, U2N3, UN2)
3.4 PHOSPHIDES
3.4.1 Boron Phosphide (BP)
3.4.2 Uranium Phosphide (UP)
3.5 CARBIDES
3.5.1 Boron Carbide (B4C)
3.5.2 Silicon Carbides (α- and β-SiC)
3.5.3 Molybdenum Carbides (Mo2C, Mo3C2)
3.6 BORIDES
3.6.1 Aluminum Borides (AlB2, AlB12)
3.6.2 Zirconium Diboride (ZrB2)
3.6.3 Hafnium Diboride (HfB2)
3.6.4 Niobium Diboride (NbB2)
3.6.5 Tantalum Diboride (TaB2)
3.6.6 Uranium Diboride (UB2)
3.6.7 Tungsten Borides (W2B, WB, W2B5)
3.7 FLUORINE-CONTAINING POLYMERS AND LOWER FLUORIDES
3.7.1 Polytetrafluoroethene {Teflon, (C2F4)y}
3.7.2 Polycarbonmonofluoride (CF1.12)y,
3.7.3 Polydifluorosilicon {(SiF2)y}
3.7.4 Germanium Difluoride (GeF2)
3.7.5 Phosphorus Trifluoride (PF3)
3.7.6 Vanadium Trifluoride (VF3)
3.7.7 Molybdenum Trifluoride (MoF3)
3.7.8 Tungsten Pentafluoride (WF5)
3.7.9 Uranium Fluorides (UF3, UF4)
3.7.10 Cobalt Difluoride (CoF2)
3.8 SILICIDES
3.8.1 Molybdenum Silicides (MoSi2, Mo3Si, Mo5Si3)
3.8.2 Tungsten Silicides (WSi2, W5Si33)
3.8.3 Uranium Silicide (U3Si)
3.9 SELENIDES
3.9.1 Lithium Selenide (Li2Se)
3.9.2 Germanium (II) Selenide (GeSe)
3.9.3 Germanium (IV) Diselenide (GeSe2, cr and vit)
3.9.4 Silicon Diselenides (SiSe2-δ)
3.9.5 Arsenic Selenide (As2Se3, cr and vit)
3.9.6 Molybdenum Selenides (MoSe2, Mo6Se6)
3.9.7 Tungsten Selenide (WSe2)
3.10 TELLURIDES
3.10.1 Silicon Telluride (Si2Te3)
3.10.2 Germanium Telluride (GeTe)
3.10.3 Zirconium Telluride (ZrTe2)
3.10.4 Molybdenum Telluride (MoTe2)
3.10.5 Tungsten Telluride (WTe2)
3.10.6 Rare-Earth Chalcogenides
3.11 MISCELLANEOUS SUBSTANCES
3.11.1 Ammonia (NH3)
3.11.2 Methane (CH4)
3.11.3 Sodium Nitrate (NaNO3)
3.11.4 Uranium Hexapalladate (U2Pd6)
3.11.5 Zirconium and Hafnium Platinides (ZrPt3, HfPt3)
3.11.6 Ternary and Quaternary Compounds
3.12 SUMMARY
4. ENTHALPIES OF FLUORINATION FROM FLUORINE-CONTAINING OXIDIZERS OTHER THAN FLUORINE GAS
4.1 REACTIONS WITH OXYGEN DIFLUORIDE (OF2)
4.2 REACTIONS WITH CHLORINE FLUORIDES (ClF, ClF3, ClF5)
4.3 REACTIONS THAT INVOLVED XENON FLUORIDE AS OXIDIZING AGENT
4.3.1 Phosphorus Trifluoride and Xenon Fluorides
4.3.2 Crystalline Substances and Xenon Difluoride
4.4 REACTIONS WITH NITROGEN FLUORIDES
4.4.1 Nitrogen Trifluoride (NF3)
4.4.2 Miscellaneous Nitrogen Fluorides
4.5 FLUOROCARBONS
4.6 FLUORIDES OF BORON, SILICON, AND SULFUR
4.7 SUMMARY
References to Part Two
Appendix
Index