Preface to second edition page xii
Preface to first edition xiii
1 Basic concepts of thermodynamics
1.1 External state variables
1.2 Internal state variables
1.3 The first law of thermodynamics
1.4 Freezing-in conditions
1.5 Reversible and irreversible processes
1.6 Second law of thermodynamics
1.7 Condition of internal equilibrium
1.8 Driving force
1.9 Combined first and second law
1.10 General conditions of equilibrium
1.11 Characteristic state functions
1.12 Entropy
2 Manipulation of thermodynamic quantities
2.1 Evaluation of one characteristic state function from another
2.2 Internal variables at equilibrium
2.3 Equations of state
2.4 Experimental conditions
2.5 Notation for partial derivatives
2.6 Use of various derivatives
2.7 Comparison between CV and CP
2.8 Change of independent variables
2.9 Maxwell relations
3 Systems with variable composition
3.1 Chemical potential
3.2 Molar and integral quantities
3.3 More about characteristic state functions
3.4 Additivity of extensive quantities. Free energy and exergy
3.5 Various forms of the combined law
3.6 Calculation of equilibrium
3.7 Evaluation of the driving force
3.8 Driving force for molecular reactions
3.9 Evaluation of integrated driving force as function of
T or P
3.10 Effective driving force
4 Practical handling of multicomponent systems
4.1 Partial quantities
4.2 Relations for partial quantities
4.3 Alternative variables for composition
4.4 The lever rule
4.5 The tie-line rule
4.6 Different sets of components
4.7 Constitution and constituents
4.8 Chemical potentials in a phase with sublattices
5 Thermodynamics of processes
5.1 Thermodynamic treatment of kinetics of
internal processes
5.2 Transformation of the set of processes
5.3 Alternative methods of transformation
5.4 Basic thermodynamic considerations for processes
5.5 Homogeneous chemical reactions
5.6 Transport processes in discontinuous systems
5.7 Transport processes in continuous systems
5.8 Substitutional diffusion
5.9 Onsager`s extremum principle
6 Stability
6.1 Introduction
6.2 Some necessary conditions of stability
6.3 Sufficient conditions of stability
6.4 Summary of stability conditions
6.5 Limit of stability
6.6 Limit of stability against fluctuations in composition
6.7 Chemical capacitance
6.8 Limit of stability against fluctuations of
internal variables
6.9 Le Chatelier`s principle
7 Applications of molar Gibbs energy diagrams
7.1 Molar Gibbs energy diagrams for binary systems
7.2 Instability of binary solutions
7.3 Illustration of the Gibbs–Duhem relation
7.4 Two-phase equilibria in binary systems
7.5 Allotropic phase boundaries
7.6 Effect of a pressure difference on a two-phase
equilibrium
7.7 Driving force for the formation of a new phase
7.8 Partitionless transformation under local equilibrium
7.9 Activation energy for a fluctuation
7.10 Ternary systems
7.11 Solubility product
8 Phase equilibria and potential phase diagrams
8.1 Gibbs` phase rule
8.2 Fundamental property diagram
8.3 Topology of potential phase diagrams
8.4 Potential phase diagrams in binary and multinary systems
8.5 Sections of potential phase diagrams
8.6 Binary systems
8.7 Ternary systems
8.8 Direction of phase fields in potential phase diagrams
8.9 Extremum in temperature and pressure
9 Molar phase diagrams
9.1 Molar axes
9.2 Sets of conjugate pairs containing molar variables
9.3 Phase boundaries
9.4 Sections of molar phase diagrams
9.5 Schreinemakers` rule
9.6 Topology of sectioned molar diagrams
10 Projected and mixed phase diagrams
10.1 Schreinemakers` projection of potential phase diagrams
10.2 The phase field rule and projected diagrams
10.3 Relation between molar diagrams and Schreinemakers`
projected diagrams
10.4 Coincidence of projected surfaces
10.5 Projection of higher-order invariant equilibria
10.6 The phase field rule and mixed diagrams
10.7 Selection of axes in mixed diagrams
10.8 Konovalov`s rule
10.9 General rule for singular equilibria
11 Direction of phase boundaries
11.1 Use of distribution coefficient
11.2 Calculation of allotropic phase boundaries
11.3 Variation of a chemical potential in a two-phase field
11.4 Direction of phase boundaries
11.5 Congruent melting points
11.6 Vertical phase boundaries
11.7 Slope of phase boundaries in isothermal sections
11.8 The effect of a pressure difference between two phases
12 Sharp and gradual phase transformations
12.1 Experimental conditions
12.2 Characterization of phase transformations
12.3 Microstructural character
12.4 Phase transformations in alloys
12.5 Classification of sharp phase transformations
12.6 Applications of Schreinemakers` projection
12.7 Scheil`s reaction diagram
12.8 Gradual phase transformations at fixed composition
12.9 Phase transformations controlled by a chemical potential
13 Transformations in closed systems
13.1 The phase field rule at constant composition
13.2 Reaction coefficients in sharp transformations
for p = c +
13.3 Graphical evaluation of reaction coefficients
13.4 Reaction coefficients in gradual transformations
for p = c
13.5 Driving force for sharp phase transformations
13.6 Driving force under constant chemical potential
13.7 Reaction coefficients at constant chemical potential
13.8 Compositional degeneracies for p = c
13.9 Effect of two compositional degeneracies for p = c .
14 Partitionless transformations
14.1 Deviation from local equilibrium
14.2 Adiabatic phase transformation
14.3 Quasi-adiabatic phase transformation
14.4 Partitionless transformations in binary system
14.5 Partial chemical equilibrium
14.6 Transformations in steel under quasi-paraequilibrium
14.7 Transformations in steel under partitioning of alloying elements
15 Limit of stability and critical phenomena
15.1 Transformations and transitions
15.2 Order–disorder transitions
15.3 Miscibility gaps
15.4 Spinodal decomposition
15.5 Tri-critical points
16 Interfaces
16.1 Surface energy and surface stress
16.2 Phase equilibrium at curved interfaces
16.3 Phase equilibrium at fluid/fluid interfaces
16.4 Size stability for spherical inclusions
16.5 Nucleation
16.6 Phase equilibrium at crystal/fluid interface
16.7 Equilibrium at curved interfaces with regard to composition
16.8 Equilibrium for crystalline inclusions with regard to composition
16.9 Surface segregation
16.10 Coherency within a phase
16.11 Coherency between two phases
16.12 Solute drag
17 Kinetics of transport processes
17.1 Thermal activation
17.2 Diffusion coefficients
17.3 Stationary states for transport processes
17.4 Local volume change
17.5 Composition of material crossing an interface
17.6 Mechanisms of interface migration
17.7 Balance of forces and dissipation
18 Methods of modelling
18.1 General principles
18.2 Choice of characteristic state function
18.3 Reference states
18.4 Representation of Gibbs energy of formation
18.5 Use of power series in T
18.6 Representation of pressure dependence
18.7 Application of physical models
18.8 Ideal gas
18.9 Real gases
18.10 Mixtures of gas species
18.11 Black-body radiation
18.12 Electron gas
19 Modelling of disorder
19.1 Introduction
19.2 Thermal vacancies in a crystal
19.3 Topological disorder
19.4 Heat capacity due to thermal vibrations
19.5 Magnetic contribution to thermodynamic properties
19.6 A simple physical model for the magnetic contribution
19.7 Random mixture of atoms
19.8 Restricted random mixture
19.9 Crystals with stoichiometric vacancies
19.10 Interstitial solutions
20 Mathematical modelling of solution phases
20.1 Ideal solution
20.2 Mixing quantities
20.3 Exc
