Definitions 1

Equilibrium:
Informal definition
In all systems there is a tendency to evolve toward states in which the properties are
determined by intrinsic factors and not by previously applied external influences. Such
simple systems states are, by definition, time independent. They are called equilibrium states.
Formal definition
Particular states of simple systems that, macroscopically, are characterized completely by the
internal energy U, and the mole numbers N1, N2,Nr of the chemical components.
(Operationally, a system is in an equilibrium state if its properties are consistently described
by thermodynamic theory).
The single, all encompassing problem of thermodynamics is the determination of the
equilibrium state that eventually results after the removal of internal constrains in a closed,
composed system.
(Herbert B. Callen, thermodynamics and an introduction to thermo-statistics).
Phase field: region of material in the phase diagram that is chemically uniform, physically
distinct, and (often) mechanically separable of other phases.
-Single phase field: Only one phase
-Two phase field: Two phases coexist
-Three phases: .
Chemical species: atoms, molecules, molecular fragments, ions, etc., subjected to a
chemical process or to a measurement.
Chemical compound: chemical substance consisting of two or more different chemical
elements that can be separated into simpler substances by chemical reactions.
Chemical component: Element contained in a phase
Solution phase: solution is a homogeneous mixture composed of only one phase. In such a
mixture, a solute is a substance dissolved in another substance, known as a solvent
Crystallisation path: Sequence of appearance of phases during cooling.
Liquidus: temperature (a curve on a phase diagram) above which a material is completely
liquid, and the maximum temperature at which crystals can co-exist with the melt
in thermodynamic equilibrium.
Solidus: temperatures (a curve on a phase diagram) below which a given substance is
completely solid (crystallized) in thermodynamic equilibrium.
Primary phase: The crystal phase that crystallizes first on cooling a substance to its liquidus
temperature.

Congruent melting: occurs during melting of a compound when the composition of the
liquid that forms is the same as the composition of the solid.
Incongruent melting: occurs when a substance does not melt uniformly and decomposes
into another substance.
Eutectic reaction: Liquid=Solid 1+ Solid 2+Solid 3+.
A liquid react at a fix temperature to yield solid phases
Peritectic reaction: L+Solid 2+Solid 3+ =Solid 1
A liquid and solid phase of fixed proportions react at a fixed temperature to yield solid phase.

Tutorial
1-Determine in the diagram de phases FeO-Fe2O3

Number and name of Phases

Number and name of Chemical Species in a solid phase and in a liquid phase
Number and name of Compound
Components of the liquid phase, wustite and hematite
Solution Phases
Range of composition and temperatures of the solution phases
Stoichiometric compounds.
I s wustite and stoichiometric compound?
Is magnetite and stoichiometric compound?
Proportion of liquid and magnetite at 1500 0C and 60 wt% of Fe2O3
Composition of phases at 1450 0C at the equilibrium liquid/magnetite
Determine the liquidus and solidus lines
Determine congruent and incongruent melting compounds points
Determine the path of crystallization from 1500 0C to 400 0C at a composition of 30
wt% of Fe2O3
Determine the path of crystallization from 1520 0C to 400 0C at a fix oxygen partial
pressure of 10-6 atm.
Draw a sequence of figures from the equilibrium between liquid/magnetite at 1450 0C
from the liquid composition to the solid magnetite composition
Design a set of experiment to determine the liquidus line for the equilibrium liquid
magnetite
What is the role of oxygen partial pressure in the Fe-O phase diagram?

Tutorial

2-Determine in the diagram de phases FeO-SiO2

Number and name of Phases

Number and name of Chemical Species in a solid phase and in a liquid phase
Number and name of Compound
Solution Phases
Stoichiometric compounds.
Proportion of liquid and wustite at 1500 K and 10 wt% of SiO2
Composition of phases at this condition
Determine the liquidus and solidus lines
Determine congruent and incongruent melting compounds points
Determine the path of crystallization from 1600 K to 1400 K at a composition of 15
wt% of SiO2 and 40 wt% of SiO2
Draw a sequence of figures from the equilibrium between liquid/wustite at 1500 K
from the liquid composition to the solid magnetite composition
Design a set of experiment to determine the liquidus line for the equilibrium
liquid/wustite
What is the role of metallic Fe in the system

3-Using the information of phase equilibria indicated on Table 1, draw a tentative phase
diagram for the system Cu2O-SiO2. Justify your assumptions, give an explanation of the
experiments (substrate, initial composition of samples) and explain the obtained phase
diagram (example, describe the eutectic point, the obtained liquidus lines).
Table 1 Experimentally determined phase compositions for the Cu2O- SiO2 system in
equilibrium with air.
Temperature [K ( oC)]

Equilibration Time (h)

1327 (1054)

1343 (1070)

1343 (1070)

1373 (1100)

1423 (1150)

1473 (1200)

1523 (1250)

1523 (1250)

1573 (1300)

1573 (1350)

12

24

12

12

12

12

12

12

12

SiO2 (wt pct)

Cu2O (wt pct)

100.0

tridymite

98.5

1.5

liquid

12.2

87.8

tridymite

98.5

1.5

liquid

12.6

87.4

tridymite

98.5

1.5

liquid

12.7

87.3

tridymite

98.4

1.6

liquid

14.0

86.0

tridymite

98.6

1.4

liquid

15.2

84.8

tridymite

98.7

1.3

liquid

16.6

83.4

tridymite

98.7

1.3

liquid

17.4

82.6

tridymite

98.8

1.2

liquid

17.5

82.5

tridymite

98.8

1.2

liquid

20.3

79.7

tridymite

98.8

1.2

Phase
cuprite