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Diagramas de equilibrio

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EQUILIBRIO

UNIDAD 1. Fundamentos Termodinámicos

DIAGRAMAS DE EQUILIBRIO

Son representaciones de temperatura (en algunas

ocasiones presión) frente a composición

Gráficamente se resumen los intervalos de temperatura (o

presión) en los que ciertas fases, o mezclas de fases, existen

en condiciones de equilibrio termodinámico

Se puede deducir el efecto de la temperatura sobre los

sólidos y las reacciones que pueden producirse entre sólidos

Se aplican en condiciones de equilibrio termodinámico, en

la práctica son muy útiles en condiciones de no equilibrio

History

In 1876 and 1878 J.Willard Gibbs published work that provides

the thermodynamic basis for understanding the equilibrium

state of any arbitrary combination of substances under

specified conditions.

However, Gibbs had been in communication with James

Clerk Maxwell, and Maxwell knew of and understood Gibbs’

work.

**Though Maxwell died only a very few years after the
**

publication of Gibbs’work, Maxwell had made known the

work to Van der Waals who in turn made it known to H.W.

Bakhuis Roozeboom.

. and a reliable Pt–Pt10%Rh thermocouple was developed by Le Chatelier in 1877. What is believed to be the first temperaturecomposition plot was made by Roberts-Austen and was published in 1875.Bakhuis Roozeboom successfully incorporated Gibbs’ concepts into his own work. the Ag–Cu system. Improvement awaited the development of a stable thermocouple. The system needs a thermocouple instead of ordinary thermometer.

austenite for the FCC-Fe solution. cementite for the Fe3C phase. and martensite for the hardening precipitate phase. pearlite for the Fe–Fe3C eutectic.Sorby was contemporaneous with Roberts-Austen and he named the phases which he observed in his metallographic studies of iron–carbon alloys as follows: Ferrite for the terminal BCC-Fe solution. Sorby chose the name austenite in honor of Roberts-Austen .

1897 Roberts-Austen diagram has been called “the first phase diagram”. . The temperature-composition diagrams of that period were plotted from dynamic measurements and the Roberts-Austen diagram was not an “equilibrium” diagram since it lacked compatibility with the equilibrium reversibility inherent in the thermodynamic constraints codified by Gibbs.

Roberts Austen invited Bakhuis Roozeboom to modify the 1899 temperature composition diagram for compatibility with the Gibbs phase rule. the path that the material should follow in transforming from initial state to equilibrium is cogent to understanding the state where it might be in a non-equilibrium “freeze” . The result was a thermodynamically valid equilibrium Fe–Fe3C diagram in 1900 Many materials are used in “frozen in” non-equilibrium states and phase diagrams provide a means of showing where the material started and where equilibrium will be reached.

**The Fe–C diagram without the metastable Fe3C has also
**

been proven useful in cast iron technology.

Sorby became aware of the Widmanstätten prints and

used an optical microscope with polished and etched

specimens to make the aforementioned study of the

microstructures of iron–carbon alloys.

Metallography, X-ray diffraction, electron and neutrón

diffraction

Thermodynamics

Internal energy. The sum of the kinetic energy (energy of

motion) and potential energy(store energy). Its

characterized solely by the state of the system

Closed system. A thermodynamic system that undergoes

no interchange of mass (material) with its surroundings,

but can interchange energy with its surroundings.

First law. (Mayer, Joule, Helmholtz)energy can be neither

created nor destroyed.

𝑑𝐸 = 𝛿𝑄 − 𝛿𝑊 or 𝑑𝐸 = 𝛿𝑄 − 𝑝𝑑𝑉

**Enthalpy. Thermal energy changes
**

under constant pressure (again

neglecting any field effects)are most

conveniently expressed in terms of

the enthalpy

Its a function of the state of the

system, as is the PV

P dV and T and P are system intensive variables . the first law of thermodynamics in differential form is dE = T dS . f.Thermodynamics The present treatment is meant only to highlight the factors that need to be taken into account when constructing or examining a phase diagram. For a system in which P dV work is the sole work contribution. For any system the number of arbitrarily alterable variables constitute the degrees of freedom.

and this in combination with thermodynamic considerations determines the constraints that are placed upon a phase diagram. n. . c. represent the number of ways in which the variables are related. Thus the number of degrees of freedom can be represented as F= n – m = c – p + 2 This is the phase rule. yield the total number of variables. The number of phases.These two plus the number of components. p. m.

.

T <Tt. Gl < Gg.Along the line defining the liquid–gas equilibrium. . the Gibbs energies of the two phases must be equal. the liquid is the stable phase so the Gibbs energy of the liquid must be lower than the Gibbs energy of the gas. so: ΔtG = ΔtH .TΔtS = 0 which leads to ΔtH/T = ΔtS At any given pressure at all temperatures below the transition temperature.

In the strictest sense. homogeneous means that the physica properties throughout the región of space occupied by the phase are absolutely identical. there are two uses of the term: the strict sense normally used by physical scientists an the somewhat looser sense normally used by materials engineers. will result in a different phase. . However. Region of space occupied by a physically homogeneous material. and any change in condition of state.Phase Phase. no matter how small.

Equilibrium There are three types of equilibria: stable. Stable equilibrium exists when the object is in its lowest energy condition Metastable equilibrium exists when additional energy must be introduced before the object can reach true stability Unstable equilibrium exist when no additional energy is needed before reaching metastability or stability . metastable. and unstable.

each unique structure consisting a distinctively separate phase. and the cristal structure of each is unique.Polymorphism The structure of solid elements and compounds under stable equilibrium condiction is crystalline. Allotrpy is usually used to describe polymorphic changes in chemical elements . Some elements and compounds are polumorphic (multishaped). their structure transforms from one cristal structure to another with changes in temperatura and pressure.

. but some (cementite) are produced at moderately slow cooling rates. Rapid freezing is a common method of producing metastable structures. metastable cristal structures can form instead of stable structures.Metastable phases Under some conditions.

Systems A physical system consists of a substance (or a group of substances) that is isolated from its surrounding (isolatedthere is no interchange of mass between the substance and its surroundings) .

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la fase líquida y la fase gaseosa .Diagrama PVT Es la representación en el espacio tridimensional Presión-Volumen específico-Temperatura de los estados posibles de un compuesto químico. Estos estados configuran en el espacio PVT una superficie discontinua. las discontinuidades a los cambios de estado que sufre el compuesto al variarse las condiciones de presión y temperatura Las superficies delimitan las zonas de existencia de a fase sólida.

DIAGRAMA PvT DE UNA SUSTANCIA PURA .

DIAGRAMA PT DE UNA SUSTANCIA PURA .

DIAGRAMA Pv DE UNA SUSTANCIA PURA .

DIAGRAMA PvT DE UNA SUSTANCIA QUE SE CONTRAE AL SOLIDIFICAR .

DIAGRAMA PT DE UNA SUSTANCIA QUE SE CONTRAE AL SOLIDIFICAR .

DIAGRAMA Pv DE UNA SUSTANCIA QUE SE CONTRAE AL SOLIDIFICAR .

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Diagrama de fases de un componente Se debe especificar el estado termodinámico de un sistema formado por una sustancia pura. dado por el número de variables intensivas independientes (grados de libertad) Se representa por el diagrama P-T conocido como diagrama de fases .

Agua .

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Azufre .

Pressure (GPa) 600 1000 1400 1800 2200 Temperatura (ºC) 2600 .

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Departamento de Ingeniería Energética y Fluidomecánica Maria Guadalupe Ordorica Morales. Termodinámica Técnica II. Antologia de la asignatura Termodinámica. . UPIBI-IPN.Referencias Tablas y diagramas. Termodinámica técnica I. 2006.

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