Calorimetry of Non-Reacting Systems

Prepared Under the Sponsorship of the International Union of Pure and Applied Chemistry Commission on Thermodynamics and the Thermochemistry

1st Edition - January 1, 1968
Editors: John P. McCullough, Donald W. Scott
Language: English
eBook ISBN:
9 7 8 - 1 - 4 8 3 2 - 2 6 7 0 - 5

Experimental Thermodynamics, Volume 1: Calorimetry of Non-Reacting Systems covers the heat capacity determinations for chemical substances in the solid, liquid, solution, and vapor… Read more

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Experimental Thermodynamics, Volume 1: Calorimetry of Non-Reacting Systems covers the heat capacity determinations for chemical substances in the solid, liquid, solution, and vapor states, at temperatures ranging from near the absolute zero to the highest at which calorimetry is feasible. This book is divided into 14 chapters. The first four chapters provide background information and general principles applicable to all types of calorimetry of non-reacting systems. The remaining 10 chapters deal with specific types of calorimetry. Most of the types of calorimetry treated are developed over a considerable period and brought to a relatively sophisticated state. For such calorimetry, the approach adopted is to give detailed accounts of a few examples of apparatus and techniques representative of the best current practice in the field. For the few types of calorimetry, a general review of the field was considered more appropriate. This book will prove useful to thermochemists, engineers, and experimentalists.

Foreword

Preface

Contributors to this Volume

Summary of Notation

1. Introduction

I. General Principles and Terminology

II. Definitions and Symbols

III. Heat Units and Constants

IV. Standard Reference Substances

V. Choice of Calorimetric Method

VI. Summary

VII. Bibliography and References

2. Temperature Scales and Temperature Measurement

I. Introduction

II. Temperature Scales

1. The Kelvin Temperature Scale

2. Practical Scales

III. Temperature Measurement

1. Liquid-in-Glass Thermometry

2. Electrical Thermometry

3. Optical Pyrometry

4. Vapor Pressure Thermometry

5. Magnetic Thermometry

IV. References

3. Energy Measurement and Standardization

I. The Problem

II. The Basis for Energy Measurement

III. The Derived Mechanical Units

IV. Working Standards for Dynamics

V. The Electrical Units

VI. Absolute Electrical Standards

VII. Standard Inductors

VIII. Absolute Determination of the Ampere

IX. Absolute Determination of the Ohm

X. Working Standards

1. Standard Resistors

2. Standard Cells

XI. Application to Thermodynamic Measurements

4. Principles of Calorimetric Design

I. Introduction

II. Chemical, Mechanical, and Electrical Considerations

1. Chemical

2. Mechanical

3. Electrical

III. Heat Flow Considerations

1. General

2. Heat Transfer by Radiation

3. Heat Transfer by Convection

4. Heat Transfer by Thermal Acoustical Oscillation

5. Heat Transfer by Mechanical Vibration

6. Heat Transfer by Conduction

IV. Applications to Calorimeter Design

1. Temperature in a Calorimeter Wall at Constant Heating Rate

2. Uncertainty in Heat Leak Due to Temperature Gradients

3. Methods of Minimizing Heat Leak Due to Temperature Gradients

4. The Calorimeter Heater Lead Problem

V. References

5. Adiabatic Low-Temperature Calorimetry

I. Introduction and Historical Survey

II. Apparatus

1. The Cryostat Environment

2. The Calorimeter Vessel

3. Measurement Techniques and Adjuvant Circuitry

III. Procedures

1. Preliminary Procedures

2. Sequence of Experiments

3. Crystallization Procedures

4. Observational Procedures

5. Melting Point and Purity Determinations

6. Studies of Polymorphic Substances

7. Vapor Pressure and Enthalpy of Vaporization Measurements

IV. Data Reductions

1. Treatment of Experimental Data

2. Reduction of Observed Data to Molal Basis

3. Smoothing the Experimental Data

4. Extrapolation of Heat Capacity Below About 10°K

5. Calculation of Thermodynamic Properties

V. General Discussion

1. Other Modes of Operation

2. Precision and Accuracy

3. Calorimetry Conference Standards

4. Comparison of Adiabatic Calorimetry with Other Methods of Calorimetry

5. Future Developments

VI. Acknowledgement

VII. References

6. Low-Temperature Calorimetry with Isothermal Shield and Evaluated Heat Leak

I. Introduction

II. Description of Typical Calorimetric Apparatus

1. General Description of a Typical Cryostat

2. A Cryostat for Calorimetry of Condensed Gases

3. Calorimeters, Thermometers, and Heaters

4. Equipment for Measurement of Resistance, Energy, and Time

5. Experimental Procedures

III. Calculation of Heat Capacity Data

1. Corrections for Heat Leak

2. Electrical Energy Measurements and Calculations

3. Correction for Heat Capacity of Empty Calorimeter, Solder, and Helium

4. Temperature Scales

5. Calculation of CP° and Other Thermodynamic Properties

6. Precision and Accuracy

IV. Acknowledgements

V. References

7. Calorimetry Below 20°K

I. Introduction

II. Cryostats for Calorimetry below 20°K

1. Cryostats for Use Between 4° and 20°K (with Possible Extension in Each Direction)

2. Cryostats for Use in the Liquid Helium Range

3. Cryostats for Measurements Below 1°K

III. Thermal Isolation of Calorimeter

IV. Methods of Cooling Calorimeters

1. With Helium Exchange Gas

2. With a Condensing Pot

3. By Waiting

4. With Mechanical Heat Switches

5. With Superconducting Heat Switches

6. Comparison of Heat Switches for Use below 1°K

V. Thermal Contact with Solid Samples

VI. Thermometry

1. Germanium Thermometers

2. Measuring Circuits for Germanium or Carbon Resistance Thermometers

3. Magnetic Thermometry

VII. Isothermal Versus Adiabatic Calorimetry

VIII. Special Techniques below 1°K

IX. References

8. High-Temperature Drop Calorimetry

I. Introduction

1. General Requirements

2. Advantages and Disadvantages of the Drop Method

II. The Furnace

1. Furnace Design and Operation

2. Temperature Measurement

3. The Sample in the Furnace

III. The Calorimeter

1. The Isothermal Calorimeter

2. The Isothermal-Jacket, Block-Type Calorimeter

IV. Treatment of the Data

1. Correcting to Standard Conditions

2. Smoothing and Representing Enthalpy Values

3. Derivation of Other Thermodynamic Properties from Relative Enthalpy

4. Precision and Accuracy

V. References

9. Adiabatic Calorimetry from 300 to 800°K

I. Introduction

1. Methods of Calorimetry Above 300°K

2. Comparison with Low-Temperature Adiabatic Calorimetry

II. Heat Exchange in Adiabatic Calorimetry

III. A High-Precision Adiabatic Calorimeter Utilizing Intermittent Heating Over the Range 300 to 800°K

1. The Calorimeter (Sample Container)

2. The Calorimeter Heater

3. The Adiabatic Shield

4. Adiabatic Shield Temperature Control

5. Environmental Control

6. Measurement of Electrical Power

7. Experimental Procedures

8. Determination of Enthalpies of Phase Transitions

9. Determination of Transition Temperatures

IV. An Adiabatic Calorimeter for Thermal Measurements from 250 to 600°K

1. Intermediate-Temperature Thermostat

2. The Silver Calorimeter

3. Operational Method

4. Calibration of Calorimeter

V. General Discussion

VI. Survey of Adiabatic Calorimeters in the Intermediate and Higher Temperature Ranges

VII. Acknowledgement

VIII. References

10. Vapor-Flow Calorimetry

I. Introduction

1. Brief Survey

2. Constant Flow Methods

II. Non-Adiabatic Calorimeters

1. Apparatus

2. Operating Procedures

3. Calculation of Experimental Results

4. Derived Results

III. Discussion

1. Accuracy of Results

2. Reference Substances

IV. References

11. Calorimetry of Saturated Fluids Including Determination of Enthalpies of Vaporization

I. Introduction

II. Theory of the Method

III. General Calorimetric Design and Procedures

IV. Calorimeters for Measuring Properties of Water

1. Calorimeter for 0-270°C

2. Calorimeter for 100-374°C

3. Calorimeter for 0-100°C

4. Comparison of Results with the Three Calorimeters

V. Calorimeter for Hydrocarbons

VI. Other Calorimetric Methods for Measuring Enthalpy of Vaporization

VII. Summary

VIII. References

12. Heat Capacity of Liquids and Solutions Near Room Temperature

I. Survey of Experimental Methods

1. General Considerations

2. Methods of Limited Precision

II. Adiabatic Heating Methods

1. Theoretical Introduction

2. Calorimeter Vessels

3. Adiabatic Shields and Regulators

4. Control Thermocouples for Adiabatic Shields

5. Experimental Procedure

III. Isothermal Drop Calorimetry

1. Introduction

2. Isothermal Drop Calorimeter Receivers

3. Drop Calorimeter Furnaces and Vessels

4. Procedure and Calculations

IV. References

13. Calorimetric Studies of Some Physical Phenomena at Low Temperatures

I. Introduction

II. Thermodynamic Properties of Films Adsorbed on Solids

1. Measurable Quantities

2. Adsorption Calorimeters of Moderate Precision

3. High Precision Adiabatic Calorimeters

4. Measurements at Liquid Helium Temperatures

III. Particle Size Effects

1. Heat Conduction Between Solid Particles

2. Calorimetric Measurements

IV. Stored Energy Experiments

1. General Remarks

2. Radiation Damage at Low Temperatures

3. Clustering in Alloys

14. High-Speed Thermodynamic Measurements and Related Techniques

I. Introduction

II. Generation of Heat

1. General Considerations

2 Heating by Electrical Pulses

3. Heating by Pulsed Radiation

4. Electrical Circuitry Associated with Single Pulse Generators

III. Measurement of Heat

1. General Considerations

2. Current Measurements

3. Voltage Measurements

4. Conclusions Regarding Measurement of Heat

IV. Measurement of Temperature

1. General Considerations

2. Photoelectric Temperature Measurement Techniques

3. Photographic Temperature Measurement Techniques

4. Other Temperature Measurement Techniques

V. Other Measurements

1. High-Speed Photographic Techniques

2. Dynamic Pressure Measurement Techniques

3. X-Ray and Interferometric Techniques for Density and Velocity Measurements

VI. Applications of High-Speed Measurements

1. General Considerations

2. Measurement of Properties

3. Other Applications

VII. Appendices

VIII. References

Author Index

Subject Index