Multiphase Systems

Dr. Rakesh Kumar Maurya

Associate Professor
Department of Mechanical Engineering
Indian Institute of Technology Ropar
IIT Ropar
Rupnagar, India (140001)
THE ENTROPY MAXIMUM AND ENERGY MINIMUM PRINCIPLES

Experience shows us that an isolated system

can behave in one of two ways:
1.Its state remains unchanged regardless of the
observation time interval; this state is said to be
one of stable equilibrium.
2. Its state changes by chance or is triggered by
a "disturbance" that is sufficiently weak to qualify
as a zero-energy interaction.

the vicinity of a stable equilibrium state in an

isolated system:
The system was initially in a state of constrained equilibrium, a
change of state took place when the internal constraint was
removed, and, eventually, the system settled in a state of
equilibrium without any internal constraints. Experience
teaches us that this final state is one of stable equilibrium.
The change of state was triggered by a sudden modificationin
the internal geometry of the isolated system

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Generalized System
These observations can be generalized for systems whose internal
constitution depends initially on an arbitrary number of internal
constraints. The geometry of the isolated system at equilibrium is
described by a number of deformation parameters, Xk.
The Xk set of deformation parameters of the general system is shown
attached to the vertical axis in Fig.
The drawing is meant to suggest that the bottom plane corresponds to
the configuration in which the system is free of internal constraints; in
other words, the bottom plane is the locus of stable equilibrium states.

As an alternative, consider closed systems that are only

incapable of work transfer. These are not isolated systems.

the constant-S plane

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THE ENERGY MINIMUM PRINCIPLE (fixed volme)
The positive slope and curvature of the U(S) curves in the
horizontal plane are tied to the internal stability conditions

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The Enthalpy Minimum

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The Helmholtz Free-Energy Minimum

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The Gibbs Free-Energy Minimum

The Gibbs free energy of the unconstrained equilibrium state

approached while in equilibrium with the temperature
reservoir (T) and pressure reservoir (P)is a minimum

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The Star Diagram

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THE STABILITY OF A SIMPLE SYSTEM- Thermal Stability

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Mechanical Stability
The partition is a diathermal piston that slides freely
during the process 1→2: that is, after the locking
mechanism is disengaged. The temperature of the entire
system is maintained uniform by contact with the
reservoir (T). The total volume of the system does not
change

energy minimum principle that applies at constant T and V is

that of minimum Helmholtz free energy

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Mechanical Stability

n conclusion, the internal mechanical stability of the system is

assured by a positive isothermal compressibility value𝜅: that is,
by the system property to contract upon pressurization at
constant temperature.

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Chemical Stability
The remaining question is what condition must be met for the simple system not to segregate
spontaneously into two or more subsystems with different chemical composition.

Held constant and uniform during the

same process are the temperature and
pressure of the system. This is the result of
the intimate contact maintained with
Reservoirs T and P.

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Chemical Stability

The simple system is chemically stable at state 2

because it has the property that the chemical
potential of species i increases when a new quantity
of that species is added to the mixture system under
conditions of constant temperature, pressure, and
mole numbers of species j.

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Stability of thermodynamic systems

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Stability of thermodynamic systems

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Stability: higher dimensions

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Stability conditions in the energy representation

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Stability conditions for other thermodynamic potentials

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ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar
ME579-Advanced Thermodynamics Rakesh K Maurya @ IIT Ropar