Combustion Calorimetry

Combustion Calorimetry deals with expertise knowledge concerning the calorimetry of combustion reactions of an element or compound. After defining the use of units and physical constants, the book discusses the basic principles of combustion calorimetry and the various instruments and calorimeters used in the experiments to measure operations concerning temperatures and its time variations. One paper discusses the theory and design criteria of combustion calorimeter calibration. Another paper discusses the results obtained from a combustion calorimeter after it has measured the energy or enthalpy of combustion of an element or compound. The book then presents the need to define accurately the exact process in which a measured energy or enthalpy change is acknowledged. One paper then presents how to find an assessment of uncertainty for any experimentally determined value through analysis of random errors and the propagation of errors. Several papers discuss the combustion calorimetry of metals, of organometallic compounds, and of fluorine. One paper presents the technological applications of heat reaction especially in the design of a chemical production plant where a reactor volume should desirably be least expensive. The book then discusses the trends in combustion calorimetry such as the prevalence of a miniaturized bomb combustion calorimetry. This volume will be beneficial to researches, technicians, and scientists in the field of catalysis, biochemistry, synthetic chemistry, and medicine.

Contributors

Key to Notation

Acknowledgments

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 Calofimetric 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 AH°f

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 Sulfur

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 (IA)

Copper, Silver, and Gold (IB)

Zinc, Cadmium, and Mercury (IIB)

Aluminum, Scandium, Yttrium and the Lanthanide's (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 Aaryl-lead Compounds

Dimanganese Decacarbonyl

Alkyl- and Ary1-germanium Compounds

Bis (Dithio-acetylacetonato ) Cobalt(II) and Nicke (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

Glove Boxes

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

Inter-comparison 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

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

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

H.C. Dickinson

T.W. Richards

W.A. Roth

W. Swietoslawski

P.E. Verkade

Acceptance of Benzoic Acid as a Bomb Calorimetric Standard

Contributions by Washburn and Rossini

E.W. Washburn

F.D. 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

Experimental Chemical Thermodynamics

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