Page 8 - Chemical equilibria Volume 4

vi Chemical Equilibria
1.5.2. Heat of transformation at constant
volume and temperature .............................. 16
1.5.3. Variations in the heat of
transformation at constant pressure with
changing temperature – Kirchhoff relation ................... 17
1.6. Set of points representing the equilibrium
states of a transformation .............................. 18
1.7. Closed systems accommodating multiple reactions ............ 19
1.8. Direction of evolution and equilibrium
conditions in an open system ............................ 20
1.9. Azeotropic transformations .......................... 21

Chapter 2. Properties of States of
Physico-Chemical Equilibrium .......................... 25
2.1. Laws of displacement of an equilibrium ................... 25
2.1.1. General form of the displacement laws ................. 25
2.1.2. Influence of a temperature disturbance ................. 26
2.1.3. Influence of a pressure disturbance ................... 27
2.1.4. Influence of the addition of a component ................ 27
2.1.5. Influence of the addition of an inert component ............ 32
2.2. Properties of all the equilibria in a system .................. 33
2.2.1. Property of the set of balance
equations of a system ............................... 34
2.2.2. Linear combinations of balance equations ............... 36
2.2.3. Base of the vector space of the balance
equations – Jouguet criteria ............................ 37
2.3. Phase laws .................................... 41
2.3.1. Reminder of Gibbs’ phase rule ...................... 41
2.3.2. Duhem’s phase rule in closed systems ................. 42
2.3.3. Comparison between the Gibbs variance
and the Duhem variance .............................. 44
2.4. Indifferent states ................................. 44
2.4.1. Definition .................................. 45
2.4.2. Condition of indifference of a state ................... 45
2.4.3. Set of indifferent points of equilibrium ................. 47
2.4.4. Gibbs–Konovalov theorem ........................ 47
2.5. Thermodynamically-equivalent systems ................... 48
2.6. Stability of equilibria .............................. 48
2.6.1. De Donder’s general stability condition ................ 49
2.6.2. Stability of a system with unilateral variations............. 49
2.6.3. Stability of a system with bilateral variations ............. 51