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Combustion Calorimetry
Experimental Chemical Thermodynamics
1st Edition - January 1, 1979
Editors: Stig Sunner, Margret Månsson
eBook ISBN:
9 7 8 - 1 - 4 8 3 2 - 8 0 8 9 - 9
Experimental Chemical Thermodynamics, Volume 1: Combustion Calorimetry covers the advances in calorimetric study of combustion, with particular emphasis on the accuracy of the… Read more
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Experimental Chemical Thermodynamics, Volume 1: Combustion Calorimetry covers the advances in calorimetric study of combustion, with particular emphasis on the accuracy of the method. This book is composed of 18 chapters, and begins with a presentation of the units and physical constants with the basic units of measurements. The succeeding chapters deal with basic principles of combustion calorimetry, emphasizing the underlying basic principles of measurement. These topics are followed by discussions on calibration of combustion calorimeters, test and auxiliary substances in combustion calorimetry, strategies in the calculation of standard-state energies of combustion from the experimentally determined quantities, and assignment of uncertainties. The final chapter considers the history of combustion calorimetry. This book will prove useful to combustion chemists and engineers, as well as researchers in the allied fields.
Contributors
Key to Notation
Acknowledgements
Foreword
Introduction
1. Units and Physical Constants
Basic units of measurements
Scale of temperature
Scale of atomic weights
Unit of energy
Physical constants
References
2. Basic Principles of Combustion Calorimetry
Introduction
The calorimeter
Adiabatic calorimeters
Isoperibol calorimeters
Heat-flow calorimeters
The calorimetric experiment
Standard-state energies of combustion
The adiabatic temperature rise
The heat-exchange equation
Calculation of the correction for heat exchange
The final temperature of an experiment
Comments on the measurement and control of temperature
References
3. Calibration of Combustion Calorimeters
Theory and design criteria
Calculation of the adiabatic temperature rise
Isoperibol calorimetry
Other types of calorimetry
Calibration with certified reference materials
Electrical calibration
References
4. Test and Auxiliary Substances in Combustion Calorimetry
Introduction
The role of test substances
The role of auxiliary substances
Characteristics of test and auxiliary substances
Desirable properties for test substances
Desirable properties for auxiliary substances
Selected test and auxiliary substances
"Recommended" and "candidate" test substances
Sources of recommended values in tables 1 and 2
Typical auxiliary substances
Needs for further test substances
References
5. Strategies in the Calculation of Standard-state Energies of Combustion from the Experimentally Determined Quantities
Introduction
Principles and general considerations
General scheme
Processes involved
Significance of terms under varying conditions
Auxiliary quantities and uncertainties
Strategies in setting up a reduction scheme
Combustion of a solid to a solid product
Combustion of a solid to a gaseous product
Combustions with two-phase reactant or product
Combustions with a bomb liquid present
Thermodynamic states
Standard states
Reference states
Bomb states
Reactions other than the main combustion reaction
Auxiliary materials
Impurities and products from incomplete combustion
Auxiliary reactions
Side reactions
Blank experiments
Calibrations
Calibration with certified reference materials under non-certification conditions
Comparison experiments
Test substances and test reactions
Bookkeeping
Equilibrium between and within phases
Specification of the bomb systems
Single-phase equilibria - condensed phase
Single-phase equilibria - gaseous phase
Two-phase equilibria
Reduction processes
Choice of path
Constant volume and constant pressure processes
Compression and decompression processes
Mixing and unmixing processes
Dilution and concentration processes
Dissociation (ionization) and association processes
Vaporization and condensation processes
Solution and desolution processes
Adsorption and desorption processes
Computer programs
Presentation of results
Appendix : Auxiliary quantities for the reductions to standard states
References
Washburn reduction schemes in the literature
General references
6. Assignment of Uncertainties
Introduction
Random errors
Precision of the experimental process
Properties of the mean
Propagation of errors
Random errors
Systematic errors
The uncertainty interval and the expression of uncertainties of results
An example of assignment of overall random uncertainty to a value of AHf
Replication uncertainty in the specific standard energy of combustion
The total experimental random uncertainty
The overall random uncertainty
The standard enthalpy of formation
Symbols used on pages 6-17 through 6-22
References
Appendix : Comments from a Compiler
7. Presentation of Combustion Calorimetric Data in the Primary Literature
Historical perspective
Introduction
Description of experimental procedure
Definition of the system studied
Performance of the calorimetric system
Reduction of experimental results
Presentation of numerical results
Derived quantities
Assignment of uncertainties
Symbols , units, and nomenclature
Discussion
References
8. General Techniques for Combustion of liquid/solid organic compounds by oxygen bomb calorimetry
The sample
Measurement of purity
Preparation for combustion
Physical state
Mass
The combustion process
The bomb and its fittings
Addition of other reagents to the bomb
Oxygen
Ignition
Calorimetry
Analysis of products
Examination for soot, carbon monoxide , and unburnt substance
Determination of carbon dioxide
Determination of oxides and oxyacids of nitrogen
References
9. Combustion of Liquid/Solid Organic Compounds with Non-Metallic Hetero-Atoms
Introduction
Compounds containing nitrogen
Compounds containing sulphur
Compounds containing fluorine
Compounds containing chlorine
Compounds containing bromine
Compounds containing iodine
Compounds containing boron
Compounds containing silicon
Compounds containing phosphorus
Compounds containing arsenic
Compounds containing selenium
References
10. Combustion Calorimetry of Metals and Simple Metallic Compounds
Introduction
Calorimetric considerations
Chemical considerations
The sample
The oxygen
Ignition
The container
Getting the right reaction
Determining the amount of reaction
Side reactions
The thermodynamic state of the reactants and the products
Calculations
Metals whose energies of combustion have been measured
Group I
Group II
Group III
Group IV
Group V
Group VI
Group VII
Group VIII
Some metallic compounds whose energies of combustion have been measured
Oxides
Carbides
Nitrides
Comparison of results : oxygen bomb calorimetry and fluorine bomb calorimetry
References
11. Combustion Calorimetry of Organometallic Compounds
Introduction
Static bomb combustion studies
Alkali metals (lA)
Copper , silver, and gold (IB)
Zinc, cadmium, and mercury (IIB)
Aluminium , scandium, yttrium and the lanthanides (IIIA)
Gallium, indium and thallium (IIIB)
Titanium , zirconium, and hafnium (IVA)
Germanium , tin, and lead (IVB)
Vanadium , niobium, and tantalum (VA)
Antimony and bismuth (VB)
Chromium , molybdenum , and tungsten (VIA)
Manganese and rhenium (VIIA)
Iron, cobalt, and nickel (VIII)
Rotating bomb combustion studies
Alkyl- and aryl-lead compounds
Dimanganese decacarbonyl
Alkyl- and ary1-germanium compounds
Bis (dithio-acetylacetonato) cobalt(II) and nickel(II)
General assessment of bomb combustion methods
The strengths of metal-carbon bonds
References
12. Combustion in Fluorine and Other Halogens
Introduction
General problems
Safety
Fluorine
Materials of construction and passivation of apparatus
The calorimeter and its calibration
Reaction vessels
One-compartment bombs
Two-compartment reaction vessels
Auxiliary apparatus
Bomb charging and discharging manifolds
Exploratory reaction vessels
Gloveboxes
Experimental techniques
Ignition of sample and combustion aids
Sample arrangements and associated problems
Analyses
Test substances
Correction to standard-state conditions
Discussion
References
13. Bomb Combustion of Gaseous Compounds in Oxygen
Introduction
Principal features of the bomb method
Calorimetric equipment and technique
Chemistry of the combustion reaction
Thermodynamic states and appropriate thermal corrections
Intercomparison of results
Conclusion
References
14. Oxygen Flame calorimetry
Introduction
Apparatus
The burner vessel
Ignition system
Calorimeter assembly
Inlet-gas purification lines
Sample inlet system
Analysis of the products
Calibration
Calibration with electrical energy
Calibration by combustion of hydrogen in oxygen
Enthalpies of combustion of CH and CHO compounds
Procedure for combustion experiments
Ignition energy
Amount of reaction and completeness of combustion
Calculation of the standard enthalphy of combustion
Enthalpies of combustion of compounds containing nitrogen
Enthalpies of combustion of compounds containing chlorine
The combustion-reaction vessel
Chemical procedure and analysis of products
Calculation of the standard enthalpy of combustion
Summary of results obtained by flame calorimetry
References
15. Fluorine Flame Calorimetry
Introduction
The need for gas-flow calorimetry of fluorine compounds
Experiment types
Special technical problems
Safe use of fluorine
Effects of corrosive action
Materials of construction
Chemical and thermodynamic description of the process
Instrumentation
Calorimeter
Reaction vessel
Burner design and flame ignition
Flow systems
Gas sample containers
Special calibration problems
Specific applications
One - phase procedures
Two-phase procedures
Experimental evaluation of reaction enthalpies
Validity of the corrosion correction
Assessment of errors
Perspective on future measurements
References
16. Combustion Calorimetry as a Technological Service
Introduction
The technological importance of heats of reaction
The significance of combustion calorimetry in industrial practice
Calorific values of gases
Definition of calorific values
Types of calorimeters
Practical examples
Calorific values of solids and liquids
Definitions of calorific values
Instrumentation
Practical examples
Methods for precision combustion calorimetry
Practical examples of the use of precision combustion calorimetry
Cyclodimerization of styrene
1,4-Butanediol diacetate by addition of acetic acid to 1,3-butadiene and hydrolysis to 1,4-butanediol and tetrahydrofuran
A process for producing caprolactam
Acknowledgment
References
17. Trends in Combustion Calorimetry
17:1 Aneroid bomb combustion calorimetry
Introduction
Static calorimeters
Rotating calorimeters
Aneroid micro calorimeters
Calorimeter design
References
17:2 Miniaturization of Bomb Combustion Calorimetry
Introduction
The calorimeter
The chemistry of the bomb process
Amount of reaction
Bomb volume
Encapsulation techniques
References
17:3 The Use of the Tian-Calvet Microcalorimeter for Combustion Measurements
18. From the History of Combustion Calorimetry
Introduction
Contributions by Thomsen
Contributions by Berthelot
Contributions by Stohmann
The evolution of combustion bombs
Electrical calibration of bomb calorimeters
Contributions by some prominent calorimetrists, 1910 to 1930
Acceptance of benzoic acid as a bomb calorimetric standard
Contributions by Washburn and Rossini
Novel developments in combustion calorimetry
Problems with compounds containing sulfur and halogens
Moving-bomb methods
Fluorine combustion calorimetry
Conclusions
Habitat of some prominent scientists in the history of combustion calorimetry
References
Additional references relevant to combustion calorimetry through 1930
- No. of pages: 454
- Language: English
- Published: January 1, 1979
- Imprint: Pergamon
- eBook ISBN: 9781483280899