| |
| |
Notation | |
| |
| |
| |
Introduction | |
| |
| |
| |
The scope and nature of chemical thermodynamics | |
| |
| |
| |
Equilibrium in mechanical systems | |
| |
| |
| |
Reversibility and equilibrium | |
| |
| |
| |
Why we need thermodynamics | |
| |
| |
| |
The mole | |
| |
| |
| |
The perfect gas | |
| |
| |
| |
Energy | |
| |
| |
| |
Work | |
| |
| |
| |
Heat and temperature | |
| |
| |
| |
Measurement of temperature | |
| |
| |
| |
Heat and molecular motion | |
| |
| |
| |
Conservation of energy | |
| |
| |
| |
State functions: a digression | |
| |
| |
| |
Enthalpy | |
| |
| |
| |
Heat capacity | |
| |
| |
Problems | |
| |
| |
| |
Entropy and equilibrium | |
| |
| |
| |
Reversibility and equilibrium: a recapitulation | |
| |
| |
| |
Condition of equilibrium | |
| |
| |
| |
Entropy | |
| |
| |
| |
Entropy as a state function | |
| |
| |
| |
Entropy of expansion of a gas | |
| |
| |
| |
Entropy changes accompanying heat flow | |
| |
| |
| |
Entropy and equilibrium | |
| |
| |
| |
A cosmological aside | |
| |
| |
| |
Entropy as a function of pressure and temperature | |
| |
| |
| |
Molecular basis of entropy | |
| |
| |
| |
Statistical basis of the Second Law | |
| |
| |
| |
Magnitudes of entropy changes | |
| |
| |
| |
Heat engines | |
| |
| |
Problems | |
| |
| |
| |
Equilibrium in chemical systems | |
| |
| |
| |
Free energy | |
| |
| |
| |
Gibbs free energy | |
| |
| |
| |
Pressure-dependence of free energy | |
| |
| |
| |
Temperature variation of free energy | |
| |
| |
| |
Phase equilibria | |
| |
| |
| |
Clapeyron equation | |
| |
| |
| |
Clausius-Clapeyron equation | |
| |
| |
| |
The vapour pressure of liquids | |
| |
| |
| |
Chemical potential | |
| |
| |
| |
Chemical potential and free energy | |
| |
| |
| |
Equilibrium between gaseous reactants | |
| |
| |
| |
Temperature-dependence of equilibrium constants | |
| |
| |
| |
Effect of pressure on equilibrium constants | |
| |
| |
| |
Basic results of chemical thermodynamics | |
| |
| |
| |
Le Chatelier's Principle | |
| |
| |
Problems | |
| |
| |
| |
Determination of thermodynamic quantities | |
| |
| |
| |
Hess's Law | |
| |
| |
| |
Standard enthalpies of formation | |
| |
| |
| |
Average bond energies | |
| |
| |
| |
Temperature dependence of enthalpy changes | |
| |
| |
| |
Standard free energies of formation | |
| |
| |
| |
Determination of free-energy changes | |
| |
| |
| |
Determination of entropies of substances | |
| |
| |
| |
Example of the determination of thermodynamic quantities | |
| |
| |
| |
Calculation of thermodynamic quantities at temperatures other than 298 K | |
| |
| |
| |
Ellingham diagrams | |
| |
| |
| |
Free-energy functions | |
| |
| |
Problems | |
| |
| |
| |
Ideal solutions | |
| |
| |
| |
The ideal solution | |
| |
| |
| |
Properties of truly ideal solutions | |
| |
| |
| |
Mixtures of liquids | |
| |
| |
| |
Ideal solutions of solids in liquids | |
| |
| |
| |
Ideal dilute solutions | |
| |
| |
| |
Colligative properties | |
| |
| |
| |
Freezing-point depression | |
| |
| |
| |
Elevation of boiling point | |
| |
| |
| |
Osmotic pressure | |
| |
| |
| |
Properties of the solute in dilute solutions | |
| |
| |
| |
Solubility of solids | |
| |
| |
Problems | |
| |
| |
| |
Non-ideal solutions | |
| |
| |
| |
The concept of activity | |
| |
| |
| |
Activity of solids in liquids | |
| |
| |
| |
Activity in aqueous solutions | |
| |
| |
| |
Chemical equilibria in solution | |
| |
| |
| |
Electrochemical cells | |
| |
| |
| |
Standard electrode potentials | |
| |
| |
Problems | |
| |
| |
| |
Thermodynamics of gases | |
| |
| |
| |
Expansion of a perfect gas | |
| |
| |
| |
Irreversible expansion | |
| |
| |
| |
Equation of state of gases | |
| |
| |
| |
Joule-Thomson experiment | |
| |
| |
| |
Imperfect gases: fugacity | |
| |
| |
| |
Calculation of fugacities | |
| |
| |
Problems | |
| |
| |
| |
Molecular basis of thermodynamics | |
| |
| |
| |
Energy levels | |
| |
| |
| |
Microstates | |
| |
| |
| |
The Boltzmann factor | |
| |
| |
| |
Behaviour of heat capacity | |
| |
| |
| |
Partition functions | |
| |
| |
| |
Entropy and the partition function | |
| |
| |
| |
Calculation of the translational partition function | |
| |
| |
| |
The rotational partition function | |
| |
| |
| |
Vibrational partition function | |
| |
| |
| |
Evaluation of the properties of gaseous nitrogen | |
| |
| |
| |
Chemical equilibrium | |
| |
| |
Problems | |
| |
| |
Answers to problems | |
| |
| |
| |
Thermochemical data at 298.15 K | |
| |
| |
| |
Thermodynamic data for ions in aqueous solution at 298.15 K | |
| |
| |
Further reading | |
| |
| |
Periodic table of elements | |
| |
| |
SI units and list of physical constants | |
| |
| |
Index | |