Thermodynamic Properties of Organic Compounds

Thermodynamic Properties of Organic Compounds: Estimation Methods, Principles and Practice, Revised Edition focuses on the progression of practical methods in computing the thermodynamic characteristics of organic compounds. Divided into two parts with eight chapters, the book concentrates first on the methods of estimation. Topics presented are statistical and combined thermodynamic functions; free energy change and equilibrium conversions; and estimation of thermodynamic properties. The next discussions focus on the thermodynamic properties of simple polyatomic systems by statistical thermodynamic methods. Discussed are molecular energy of an ideal gas; partition function and thermodynamic properties; and calculation of statistical thermodynamic functions. The book also notes the dynamic properties of long chain hydrocarbons and the method of structural similarity. Tabulations and numerical representations are presented as well. Discussions also focus on methods of group contributions and group equations. Included are paraffins, unsaturated carbons, cyclic hydrocarbons, and nonhydrocarbon groups. The last part of the text focuses on heat formation and heat capacity; the applications of thermodynamic method; and numerical data. Included in the discussions are bond energies and binding energies; gaseous free radicals and ions; and hydrogenation of benzene. The book is an important source of data for readers interested in studying the thermodynamic characteristics of organic compounds.

Preface to the Revised Edition

Preface to the First Edition

Part I Methods of Estimation

Chapter 1. The Free Energy Change in a Chemical Reaction

1. Chemical Thermodynamics in Research

2. Standard Free Energy Change

3. Modified van't Hoff Isochore

4. Statistical Thermodynamic Functions

5. Combined Thermodynamic Functions

6. Free Energy Change and Equilibrium Conversions

7. Effect of Pressure

8. Estimation of Thermodynamic Properties

Chapter 2. Thermodynamic Properties of Simple Polyatomic Systems by Statistical Thermodynamic Methods

1. Introduction

2. Molecular Energy of an Ideal Gas

3. Partition Function and Thermodynamic Properties

4. Rigid Rotator-Simple Vibrator

5. Calculation of Statistical Thermodynamic Functions

6. Internal Rotation

Chapter 3. Thermodynamic Properties of Long Chain Hydrocarbons

1. Introduction

2. Construction of the Correlations

3. Calculation of Thermodynamic Properties

4. Branch Chain Hydrocarbons

5. Unsaturated Hydrocarbons

6. The Steric Factor

7. Random Kinking and Ball-Like Molecules

Chapter 4. The Method of Structural Similarity

1. Introduction

2. Construction of the Correlation

3. Paraffins

4. Unsaturated Hydrocarbons

5. Cyclic Hydrocarbons

6. Organic Compounds Containing Oxygen

7. Nitrogen, Halogen, and Sulfur-Containing Organic Compounds

8. Entropy and Free Energy Regularities

Chapter 5. The Methods of Group Contributions

1. Introduction

2. Methods

3. Construction of the Correlations

4. Calculation of Thermodynamic Properties

5. Nonhydrocarbon Groups

Addendum

Chapter 6. The Method of Group Equations

1. Introduction

2. Symmetry Number

3. Internal Rotation

4. Calculation of Thermodynamic Properties

5. Extension of Thermodynamic Values from the Aliphatic to the Aromatic Series ' 95

Chapter 7. Heat of Formation and Heat Capacity

1. Introduction

2. Heat of Formation

3. Bond Energies and Binding Energies

4. Heat of Formation from Group Increments

5. Gaseous Free Radicals and Ions

6. Heat of Combustion by Group Increments

7. Heat of Vaporization

8. Heat Capacity

9. Method of Generalized Vibrational Assignments

10. Temperature Dependence of Heat Capacity

Addendum

Chapter 8. Applications of the Thermodynamic Method

1. Introduction

2. Comparison of Comprehensive Estimation Methods

3. Hydrogenation of Benzene

4. The Thermal Dimerization of Butadiene

5. Thermodynamic or Kinetic Control

6. Ring Closure

7. Cyclic Additions

8. Other Applications

Addendum

Part II Numerical Data

Table 1. Bond Energies

Table 2. Atomic Covalent Radii and Bond Angles

Table 3. A Six-Place Table of the Einstein Functions

Table 4. Restricted Internal Rotational Free Energy (— G/T)Contributions

Table 5. Free Energy Increase from Free Rotation (G — Gf)/T

Table 6. Restricted Internal Rotational Entropy Contribution (Sr,)

Table 7. Entropy Decrease from Free Rotation (Sf — Sr,)

Table 8. Restricted Internal Rotational Heat Content Contribution, (HT-H0)IT

Table 9. Restricted Internal Rotational Heat Capacity Contribution (Cp°)

Table 10. Potential Barriers Hindering Internal Rotation

Table 11. Additive Increments in Free Energy Function, — (G° — H0°)/T, of Normal Paraffins

Table 12. Additive Increments in Heat Content, (H° — H0°)/T, of Normal Paraffins

Table 13. Additive Increments in Heat Capacity, Cp°, of Normal Paraffins

Table 14. Thermodynamic Properties of Normal Heptane

Table 15. [CH2] Increment for Normal Paraffins

Table 16. Additional Increments Extending the Infinite Chain Method to Branch Chain Paraffins

Table 17. Parent Group Properties

Table 18. Contributions of Primary CH3 Substitution

Table 19. Secondary Methyl Substitutions

Table 20. Multiple Bond Contributions and Additional Corrections

Table 21. Nonhydrocarbon Group Contributions Replacing [CH3] Group

Table 22. (H° — H0°) Increments for Hydrocarbon Groups

Table 23. ΔHf° Increments for Hydrocarbon Groups

Table 24. (G° — H0°) Increments for Hydrocarbon Groups

Table 25. ΔGf° Increments for Hydrocarbon Groups

Table 26. ΔGf° and ΔHf° Increments for Nonhydrocarbon Groups

Table 27. Vibrational Group Contributions to Heat Content (Zero Pressure)

Table 28. Characteristic Internal Rotational Contributions to Heat Content (Zero Pressure)

Table 29. Vibrational Group Contributions to Heat Capacity (Zero Pressure)

Table 30. Characteristic Internal Rotational Contributions to Heat Capacity (Zero Pressure)

Table 31. Group Contributions to ΔSf° and ΔHf° (Type I Groups)

Table 32. Conjugation and Adjacency Contributions to ΔSf° and ΔHf° (Type I Groups)

Table 33. Vibrational Group Contributions to (SfT° — Sf298°) (Type II Groups)

Table 34. Characteristic Internal Rotational Contributions to (SfT° — Sf298°)

Table 35. Vibrational Group Contributions to (HfT° — Hf298°) (Type II Groups)

Table 36. Characteristic Internal Rotational Contributions to (HfT° — Hf298°)

Table 37. ΔGf° Increments for Hydrocarbon Groups

Table 38. ΔGf° Corrections for Ring Formation and Branching Effects

Table 39. ΔGf° Increments for Nonhydrocarbon Groups

Table 40. ΔGf° Parameters for Some Simple Organic and Inorganic Compounds

Table 41. ΔHf298° Group Increments for Radicals

Table 42. ΔHf298° Group Increments for Ions

Table 43. Atomic Contributions to Cp° and S° (25°C, 1 Atmos.)

Table 44. Bond Contributions to Cp°, S°, and ΔHf° at 25°C, 1 Atmos.

Table 45. Group Contributions to Cp°, 5°, and ΔHf° for Ideal Gases at 25°C, 1 Atmos. Hydrocarbons

Table 46. Group Contributions to Cp°, S°, and ΔHf° for Ideal Gases at 25°C, 1 Atmos. Halogen Compounds

Table 47. Group Contributions to Cp°, S°, and AHf° for Ideal Gases at 25°C, 1 Atmos. Miscellaneous

Table 48. Values of Group Contributions to the Heat of Formation Used in Bryant Calculations

Table 49. Values of Substitution Group Contributions to the Heat of Formation Involving the Halogens

Table 50. Log KfG for Paraffinic Groups

Table 51. Log KfG for Olefinic Groups

Table 52. Log KfG for Acetylenic Groups

Table 53. Log KfG for Conjugate Olefin Groups

Table 54. Log KfG for Aromatic Groups

Table 55. Log KfG for Oxygen-Containing Groups

Table 56. Log KfG for Nitrogen-Containing Groups

Table 57. Log KfG for Sulfur-Containing Groups

Table 58. Log KfG for Halogen-Containing Groups

Table 59. Log KfG for Some Organic Compounds

Table 60. Correction Factors for Cyclization

Table 61. Correction Factors Necessitated by Introducing Lateral Chains

Table 62. Thermodynamic Properties for n-Propyl Halides

Table 63. Aliphatic Hydrocarbon Groups

Table 64. Aromatic Hydrocarbon Groups

Table 65. Branching in Paraffin Chains

Table 66. Branching in Cycloparaffins

Table 67. Branching in Aromatics

Table 68. Ring Corrections

Table 69. Oxygen-Containing Groups

Table 70. Nitrogen- and Sulfur-Containing Groups

Table 71. Halogen-Containing Groups

Table 72. Bond Contributions for Heats of Atomization, Formation, and Combustion of Gases and Liquids

Table 73. Empirical Equations for Heat of Combustion

Table 74. Structural Correlations for Calculation of Heat of Combustion

Table 75. Atomic and Structural Parachor Contributions

Table 76. Generalized Bonding Frequencies and Constants to Evaluate Einstein Functions, (Cp°)t = ai + biT + ciT2

Table 77. Contribution of Generalized Bond Vibrational Frequencies to Heat Capacity

Table 78. Heat Capacity Solutions to Einstein Functions (One Degree of Freedom)

Author Index

Subject Index