Combustion Calorimetry

Combustion Calorimetry

Experimental Chemical Thermodynamics

1st Edition - January 1, 1979

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  • Editors: Stig Sunner, Margret Månsson
  • eBook ISBN: 9781483280899

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Description

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.

Table of Contents


  • 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

Product details

  • No. of pages: 454
  • Language: English
  • Copyright: © Pergamon 2013
  • Published: January 1, 1979
  • Imprint: Pergamon
  • eBook ISBN: 9781483280899

About the Editors

Stig Sunner

Margret Månsson

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